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Environmental Science. Processes &... Jun 2024Petroleum products in the environment can produce significant toxicity through photochemically driven processes. Burning surface oil and photochemical degradation were...
Petroleum products in the environment can produce significant toxicity through photochemically driven processes. Burning surface oil and photochemical degradation were two mechanisms for oil removal after the Deepwater Horizon (DWH) oil spill in the Gulf of Mexico. After burning, residual oil remains in the environment and may undergo further weathering, a poorly understood fate. Although photochemistry was a major degradation pathway of the DWH oil, its effect on burned oil residue in the environment is under studied. Here, we ignited Macondo surrogate crude oil and allowed it to burn to exhaustion. Water-accommodated fractions (WAFs) of the burn residue were created in full sunlight to determine the effects of photochemical weathering on the burned oil residue. Our findings show that increased dissolved organic carbon concentrations (DOC) for the light unburned and light burned after sunlight exposure positively correlated to decreased microbial growth and production inhibition ( more toxic) when compared to the dark controls. Optical and molecular analytical techniques were used to identify the classes of compounds contributing to the toxicity in the dark and light burned and dark and light unburned WAFs. After light exposure, the optical composition between the light unburned and light burned differed significantly ( < 0.05), revealing key fluorescence signatures commonly identified as crude oil degradation products. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) analysis showed more condensed aromatic, reduced oxygenated compounds present in the light burned than in the light unburned. FT-ICR MS also showed an increase in the percent relative abundance of carboxyl-rich alicyclic molecules (CRAM) like compounds in the light burned compared to light unburned. The increase in CRAM suggests that the composition of the light burned is more photorefractory, , reduced, explaining the residual toxicity observed in microbial activity. Overall, these data indicate burning removes some but not all toxic compounds, leaving behind compounds which retain considerable toxicity. This study shows that burn oil residues are photolabile breaking down further into complex reduced compounds.
PubMed: 38842096
DOI: 10.1039/d4em00023d -
Light, Science & Applications Jun 2024Imagine if it were possible to create 3D objects in the palm of your hand within seconds using only a single photonic chip. Although 3D printing has revolutionized the...
Imagine if it were possible to create 3D objects in the palm of your hand within seconds using only a single photonic chip. Although 3D printing has revolutionized the way we create in nearly every aspect of modern society, current 3D printers rely on large and complex mechanical systems to enable layer-by-layer addition of material. This limits print speed, resolution, portability, form factor, and material complexity. Although there have been recent efforts in developing novel photocuring-based 3D printers that utilize light to transform matter from liquid resins to solid objects using advanced methods, they remain reliant on bulky and complex mechanical systems. To address these limitations, we combine the fields of silicon photonics and photochemistry to propose the first chip-based 3D printer. The proposed system consists of only a single millimeter-scale photonic chip without any moving parts that emits reconfigurable visible-light holograms up into a simple stationary resin well to enable non-mechanical 3D printing. Furthermore, we experimentally demonstrate a stereolithography-inspired proof-of-concept version of the chip-based 3D printer using a visible-light beam-steering integrated optical phased array and visible-light-curable resin, showing 3D printing using a chip-based system for the first time. This work demonstrates the first steps towards a highly-compact, portable, and low-cost solution for the next generation of 3D printers.
PubMed: 38839804
DOI: 10.1038/s41377-024-01478-2 -
ACS Macro Letters Jun 2024Quantifying adhesion is crucial for understanding adhesion mechanisms and developing advanced dopamine-inspired materials and devices. However, achieving nondestructive...
Quantifying adhesion is crucial for understanding adhesion mechanisms and developing advanced dopamine-inspired materials and devices. However, achieving nondestructive and real-time quantitation of adhesion using optical spectra remains challenging. Here, we present a dopamine-inspired orthogonal phenanthrenequinone photochemistry strategy for the one-step adhesion and real-time visual quantitation of fluorescent spectra. This strategy utilizes phenanthrenequinone-mediated photochemistry to facilitate conjoined network formation in the adhesive through simultaneous photoclick cycloaddition and free-radical polymerization. The resulting hydrogel-like adhesive exhibits good mechanical performance, with a Young's modulus of 300 kPa, a toughness of 750 kJ m, and a fracture energy of 4500 J m. This adhesive, along with polycyclic aromatic phenanthrenequinones, shows strong adhesion (>100 kPa) and interfacial toughness thresholds (250 J m) on diverse surfaces─twice to triple as much as typical dopamine-contained adhesives. Importantly, such an adhesive demonstrates excellent fluorescent performance under UV irradiation, closely correlating with its adhesion strengths. Their fluorescence intensities remain constant after continuous stretching/releasing treatment and even in the dried state. Therefore, this dopamine-inspired orthogonal phenanthrenequinone photochemistry is readily available for real-time and nondestructive visual quantitation of adhesion performance under various conditions. Moreover, the adhesive precursor is chemically ultrastable for more than seven months and achieves adhesion on substrates within seconds upon blue light irradiation. As a proof-of-concept, we leverage the rapid and visual quantitation of adhesion and printability to create fluorescent patterns and structures, showcasing applications in information storage, adhesion prediction, and self-reporting properties. This general and straightforward strategy holds promise for rapidly preparing functional adhesive materials and designing high-performance wearable devices.
PubMed: 38838345
DOI: 10.1021/acsmacrolett.4c00260 -
Environmental Science & Technology Jun 2024Ground-level ozone (O) pollution has emerged as a significant concern due to its detrimental effects on human health and the ecosystem. Catalytic removal of O has proven...
Ground-level ozone (O) pollution has emerged as a significant concern due to its detrimental effects on human health and the ecosystem. Catalytic removal of O has proven to be the most efficient and cost-effective method. However, its practical application faces substantial challenges, particularly in relation to its effectiveness across the entire humidity range. Herein, we proposed a novel strategy termed "dual active sites" by employing graphitized carbon-loaded core-shell cobalt catalysts (Co@CoO-C). Co@CoO-C was synthesized via the pyrolysis of a Co-organic ligand as the precursor. By utilizing this approach, we achieved a nearly constant 100% working efficiency of the Co@CoO-C catalyst for catalyzing O decomposition across the entire humidity range. Physicochemical characterization coupled with density functional theory calculations elucidates that the presence of encapsulated metallic Co nanoparticles enhances the reactivity of the cobalt oxide capping layer. Additionally, the interface carbon atom, strongly influenced by adjacent metallic Co nuclei, functions as a secondary active site for the decomposition of O decomposition. The utilization of dual active sites effectively mitigates the competitive adsorption of HO molecules, thus isolating them for adsorption in the cobalt oxide capping layer. This optimized configuration allows for the decomposition of O without interference from moisture. Furthermore, O decomposition monolithic catalysts were synthesized using a material extrusion-based three-dimensional (3D) printing technology, which demonstrated a low pressure drop and exceptional mechanical strength. This work provides a "dual active site" strategy for the O decomposition reaction, realizing O catalytic decomposition over the entire humidity range.
PubMed: 38838084
DOI: 10.1021/acs.est.4c01527 -
Chemphyschem : a European Journal of... Jun 2024The peripherical protons of the dye molecule hypericin can undergo structural interconversion (tautomerization) between different isomers through separated by a low...
The peripherical protons of the dye molecule hypericin can undergo structural interconversion (tautomerization) between different isomers through separated by a low energy barrier with rates that depends sensitively on the interaction with local chemical environment defined by the nature of host material. We investigate the deuterium (D) isotope effect of hypericin tautomerism at the single-molecule level to avoid ensemble averaging in different polymer matrices by a combined spectroscopic and computational approach. In the 'innocent' PMMA matrix only intramolecular isotope effects on the internal conversion channel and tautomerization are observed; while PVA specifically interacts with the probe via H- and D-bonding. This establishes a single molecular picture on intra- and intermolecular nano-environment effects to control chromophore photophysics and -chemistry.
PubMed: 38837881
DOI: 10.1002/cphc.202400374 -
Chemistry (Weinheim An Der Bergstrasse,... Jun 2024Plastic pollution constitutes an evergrowing urgent environmental problem, since overaccumulation of plastic waste, arising from the immense increase of the production...
Plastic pollution constitutes an evergrowing urgent environmental problem, since overaccumulation of plastic waste, arising from the immense increase of the production of disposable plastic products, overcame planet's capacity to properly handle them. Chemical upcycling of polystyrene constitutes a convenient method for the conversion of plastic waste into high-added value chemicals, suggesting an attractive perspective in dealing with the environmental crisis. We demonstrate herein a novel, easy-to-perform organocatalytic photoinduced aerobic protocol, which proceeds via synergistic indirect hydrogen atom transfer (HAT) catalysis under LED 390 nm Kessil lamps as the irradiation source. The developed method employs a BrCH2CN-thioxanthone photocatalytic system and was successfully applied to a variety of everyday-life plastic products, leading to the isolation of benzoic acid after simple base-acid work up in yields varying from 23-49%, while a large-scale experiment was successfully performed, suggesting that the photocatalytic step is susceptible to industrial application.
PubMed: 38837489
DOI: 10.1002/chem.202401588 -
Scientific Reports Jun 2024This study introduces an evaluation methodology tailored for bioreactors, with the aim of assessing the stress experienced by algae due to harmful contaminants released...
This study introduces an evaluation methodology tailored for bioreactors, with the aim of assessing the stress experienced by algae due to harmful contaminants released from antifouling (AF) paints. We present an online monitoring system equipped with an ultra-sensitive sensor that conducts non-invasive measurements of algal culture's optical density and physiological stage through chlorophyll fluorescence signals. By coupling the ultra-sensitive sensor with flash-induced chlorophyll fluorescence, we examined the dynamic fluorescence changes in the green microalga Chlamydomonas reinhardtii when exposed to biocides. Over a 24-h observation period, increasing concentrations of biocides led to a decrease in photosynthetic activity. Notably, a substantial reduction in the maximum quantum yield of primary photochemistry (F/F) was observed within the first hour of exposure. Subsequently, we detected a partial recovery in F/F; however, this recovery remained 50% lower than that of the controls. Integrating the advanced submersible sensor with fluorescence decay kinetics offered a comprehensive perspective on the dynamic alterations in algal cells under the exposure to biocides released from antifouling coatings. The analysis of fluorescence relaxation kinetics revealed a significant shortening of the fast and middle phases, along with an increase in the duration of the slow phase, for the coating with the highest levels of biocides. Combining automated culturing and measuring methods, this approach has demonstrated its effectiveness as an ultrasensitive and non-invasive tool for monitoring the physiology of photosynthetic cultures. This is particularly valuable in the context of studying microalgae and their early responses to various environmental conditions, as well as the potential to develop an AF system with minimal harm to the environment.
Topics: Chlamydomonas reinhardtii; Bioreactors; Disinfectants; Fluorescence; Photosynthesis; Chlorophyll; Water Pollutants, Chemical
PubMed: 38834660
DOI: 10.1038/s41598-024-63631-6 -
Nature Communications Jun 2024Classical photochemistry requires nanosecond excited-state lifetimes for diffusion-controlled reactions. Excited radicals with picosecond lifetimes have been implied by...
Classical photochemistry requires nanosecond excited-state lifetimes for diffusion-controlled reactions. Excited radicals with picosecond lifetimes have been implied by numerous photoredox studies, and controversy has arisen as to whether they can actually be catalytically active. We provide direct evidence for the elusive pre-association between radical ions and substrate molecules, enabling photoinduced electron transfer beyond the diffusion limit. A strategy based on two distinct light absorbers, mimicking the natural photosystems I and II, is used to generate excited radicals, unleashing extreme reduction power and activating C(sp)-Cl and C(sp)-F bonds. Our findings provide a long-sought mechanistic understanding for many previous synthetically-oriented works and permit more rational future photoredox reaction development. The newly developed excitation strategy pushes the current limits of reactions based on multi-photon excitation and very short-lived but highly redox active species.
PubMed: 38834625
DOI: 10.1038/s41467-024-49006-5 -
The Journal of Chemical Physics Jun 2024Superfluid helium nanodroplets are unique nanomatrices for the isolation and study of transient molecular species, such as radicals, carbenes, and ions. In this work,...
Superfluid helium nanodroplets are unique nanomatrices for the isolation and study of transient molecular species, such as radicals, carbenes, and ions. In this work, isomers of C3H4+ were produced upon electron ionization of propyne and allene molecules and interrogated via infrared spectroscopy inside He nanodroplet matrices. It was found that the spectrum of C3H4+ has at least three distinct groups of bands. The relative intensities of the bands depend on the precursor employed and its pickup pressure, which indicates the presence of at least three different isomers. Two isomers were identified as allene and propyne radical cations. The third isomer, which has several new bands in the range of 3100-3200 cm-1, may be the elusive vinylmethylene H2C=CH-CH+ radical cation. The observed bands for the allene and propyne cations are in good agreement with the results of density functional theory calculations. However, there is only moderate agreement between the new bands and the theoretically calculated vinylmethylene spectrum, which indicates more work is necessary to unambiguously assign it.
PubMed: 38832743
DOI: 10.1063/5.0206412 -
RSC Advances May 2024Aliovalent doping in ceria and defect engineering are important aspects in tuning the properties of ceria for advanced technological applications, especially in the...
Aliovalent doping in ceria and defect engineering are important aspects in tuning the properties of ceria for advanced technological applications, especially in the emerging field of electrocatalytic water-splitting for harvesting renewable energy. However, the ambiguity regarding the choice of dopants/co-dopants and ways to deal with the size difference between dopants and lattice hosts remains a long-standing problem. In this study, ceria was aliovalently codoped with Sc and La while keeping the total concentration of dopants constant; the ionic radius of the former is smaller and that of the latter is larger than Ce. Variations in the relative amounts of these dopants helped to modulate the effective ionic radii and match that of the host. A systematic study on the role of these aliovalent dopants in defect evolution in ceria and in modulating the Ce fraction using powder XRD, Rietveld refinement, positron annihilation lifetime spectroscopy, X-ray photoelectron spectroscopy, Eu photoluminescence, and Raman spectroscopy is presented here. The evolved defects and their dependence on subtle factors other than charge compensation are further correlated with their electrocatalytic activity towards oxygen evolution reaction (OER) in alkaline medium. The catalyst with an optimum defect density, maximum Ce fraction at the surface and the least effective ionic radius difference between the dopants and the host demonstrated the best performance towards the OER. This study demonstrates how effective ionic radius modulation in defect-engineered ceria through a judicious choice of codopants can enhance the catalytic property of ceria and provides immensely helpful information for designing ceria-based heterogeneous catalysts with desired functionalities.
PubMed: 38832250
DOI: 10.1039/d4ra03360d