The subject of this review is the colloidal quantum dot (QD) and specifically the interaction of the QD with proximate molecules. It covers various functions of these molecules, including (i) ligands ...for the QDs, coupled electronically or vibrationally to localized surface states or to the delocalized states of the QD core, (ii) energy or electron donors or acceptors for the QDs, and (iii) structural components of QD assemblies that dictate QD–QD or QD–molecule interactions. Research on interactions of ligands with colloidal QDs has revealed that ligands determine not only the excited state dynamics of the QD but also, in some cases, its ground state electronic structure. Specifically, the article discusses (i) measurement of the electronic structure of colloidal QDs and the influence of their surface chemistry, in particular, dipolar ligands and exciton-delocalizing ligands, on their electronic energies; (ii) the role of molecules in interfacial electron and energy transfer processes involving QDs, including electron-to-vibrational energy transfer and the use of the ligand shell of a QD as a semipermeable membrane that gates its redox activity; and (iii) a particular application of colloidal QDs, photoredox catalysis, which exploits the combination of the electronic structure of the QD core and the chemistry at its surface to use the energy of the QD excited state to drive chemical reactions.
E-cigarettes are generally thought of as a safer smoking alternative to traditional cigarettes. However, little is known about the effects of e-cigarette liquids (e-liquids) on the lung. Since over ...7,000 unique flavors have been identified for purchase in the United States, our goal was to conduct a screen that would test whether different flavored e-liquids exhibited different toxicant profiles. We tested the effects of 13 different flavored e-liquids with nicotine and propylene glycol/vegetable glycerin (PG/VG) serving as controls on a lung epithelial cell line (CALU3). Using the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay as an indicator of cell proliferation/viability, we demonstrated a dose-dependent decrease of MTT metabolism by all flavors tested. However, a group of four flavors consistently showed significantly greater toxicity compared with the PG/VG control, indicating the potential for some flavors to elicit more harmful effects than others. We also tested the aerosolized "vapor" from select e-liquids on cells and found similar dose-dependent trends, suggesting that direct e-liquid exposures are a justifiable first-pass screening approach for determining relative e-liquid toxicity. We then identified individual chemical constituents for all 13 flavors using gas chromatography-mass spectrometry. These data revealed that beyond nicotine and PG/VG, the 13 flavored e-liquids have diverse chemical constituents. Since all of the flavors exhibited some degree of toxicity and a diverse array of chemical constituents with little inhalation toxicity available, we conclude that flavored e-liquids should be extensively tested on a case-by-case basis to determine the potential for toxicity in the lung and elsewhere.
We evaluated the effects of Roundup QuikPRO™ (73.3 % glyphosate) using real-world herbicide application treatments: (1) overspray (low-dose), (2) powder spill (high-dose), and (3) controls (no-dose). ...Seagrass and water quality were monitored to observe responses to acute herbicide application. Seagrass shoot densities significantly declined over time in high-dose treatments, whereas seagrass shoot densities in low-dose treatments were comparable to controls. In high-dose treatments, seagrass mortality increased over time, 100 % Halophila ovalis and 81 % Halodule wrightii mortality from day zero to 53. Collectively, glyphosate concentrations were negatively correlated with seagrass shoot densities, and positively correlated with water column nutrients (TN and TP). Based on these results we do not attribute local seagrass declines to low-dose glyphosate exposure, i.e., herbicide overspray events. However, we advise caution against improper herbicide handling, since glyphosate remained detectable in relatively high concentrations (<88 mg/L) after 53 days, resulting in seagrass mortality and increased water column nutrients.
This article reviews the mechanisms through which molecules adsorbed to the surfaces of semiconductor nanocrystals, quantum dots (QDs), influence the pathways for and dynamics of intra- and interband ...exciton relaxation in these nanostructures. In many cases, the surface chemistry of the QDs determines the competition between Auger relaxation and electronic-to-vibrational energy transfer in the intraband cooling of hot carriers, and between electron or hole-trapping processes and radiative recombination in relaxation of band-edge excitons. The latter competition determines the photoluminescence quantum yield of the nanocrystals, which is predictable through a set of mostly phenomenological models that link the surface coverage of ligands with specific chemical properties to the rate constants for nonradiative exciton decay.
The increasing focus on lipid metabolism has revealed a need for analytical techniques capable of structurally characterizing lipids with a high degree of specificity. Lipids can exist as any one of ...a large number of double bond positional isomers, which are indistinguishable by single-stage mass spectrometry alone. Ozonolysis reactions coupled to mass spectrometry have previously been demonstrated as a means for localizing double bonds in unsaturated lipids. Here we describe an online, solution-phase reactor using ozone produced via a low-pressure mercury lamp, which generates aldehyde products diagnostic of cleavage at a particular double bond position. This flow-cell device is utilized in conjunction with structurally selective ion mobility-mass spectrometry. The lamp-mediated reaction was found to be effective for multiple lipid species in both positive and negative ionization modes, and the conversion efficiency from precursor to product ions was tunable across a wide range (20–95%) by varying the flow rate through the ozonolysis device. Ion mobility separation of the ozonolysis products generated additional structural information and revealed the presence of saturated species in a complex mixture. The method presented here is simple, robust, and readily coupled to existing instrument platforms with minimal modifications necessary. For these reasons, application to standard lipidomic workflows is possible and aids in more comprehensive structural characterization of a myriad of lipid species.
Subsurface lithoautotrophic microbial ecosystems (SLiMEs) under oligotrophic conditions are typically supported by H₂. Methanogens and sulfate reducers, and the respective energy processes, are ...thought to be the dominant players and have been the research foci. Recent investigations showed that, in some deep, fluid-filled fractures in the Witwatersrand Basin, South Africa, methanogens contribute <5% of the total DNA and appear to produce sufficient CH₄ to support the rest of the diverse community. This paradoxical situation reflects our lack of knowledge about the in situ metabolic diversity and the overall ecological trophic structure of SLiMEs. Here, we show the active metabolic processes and interactions in one of these communities by combining metatranscriptomic assemblies, metaproteomic and stable isotopic data, and thermodynamic modeling. Dominating the active community are four autotrophic β-proteobacterial genera that are capable of oxidizing sulfur by denitrification, a process that was previously unnoticed in the deep subsurface. They co-occur with sulfate reducers, anaerobic methane oxidizers, and methanogens, which each comprise <5% of the total community. Syntrophic interactions between these microbial groups remove thermodynamic bottlenecks and enable diverse metabolic reactions to occur under the oligotrophic conditions that dominate in the subsurface. The dominance of sulfur oxidizers is explained by the availability of electron donors and acceptors to these microorganisms and the ability of sulfur-oxidizing denitrifiers to gain energy through concomitant S and H₂ oxidation. We demonstrate that SLiMEs support taxonomically and metabolically diverse microorganisms, which, through developing syntrophic partnerships, overcome thermodynamic barriers imposed by the environmental conditions in the deep subsurface.
Plastic pollution is a concern in many nearshore ecosystems, and it is critical to understand how microplastics (plastics <5 mm in length) affect nearshore marine biota. Here, we report the presence ...of microplastics in the benthic, upside-down jellyfish (Cassiopea xamachana) across three estuaries in south Florida. Microplastics were recovered from Cassiopea using an acid digestion, then enumerated via microscopy, and identified using micro Fourier-transform interferometer (μFTIR) analysis. Out of 115 specimens analyzed, 77% contained microplastics. Bell diameter and number of plastics per individual varied significantly across locations with the highest plastic densities and bell diameter observed in individuals from Big Pine Key, followed by Jupiter, and Sarasota. μFTIR analysis confirmed that synthetic microfibers were the dominant microplastic measured at all three locations and may indicate Cassiopea as potential sinks of microplastic. Cassiopea may be used as bioindicators of microplastic contamination in the future, allowing for potential plastic pollution mitigation.
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•Microplastics were present in C. xamachana sampled in three of Florida's estuaries.•The most common type of plastic found in C. xamachana was microfibers.•Occurrence and abundance of microplastics were significantly higher in C. xamachana from Big Pine Key, Florida.•Cassiopea xamachana could serve as a potential bioindicator of microplastics.
Leveraging the discourse of the Arab-Israeli conflict, Ibtisam Ma'arana uses the vehicle of the beauty pageant to consider the pressures on Arab and Druze women in Israeli society. In her documentary ...Lady Kul El-Arab (2008) she follows Druze Duah Fares as she participates in a small regional Arab contest and then competes in the national Miss Israel event. While the coverage of beauty competitions and the conventions of films and television programs about them have long considered the tension between female self-empowerment and exploitation, this film disrupts the usual narrative, instead drawing greater attention to nationalism and the identity politics which pageants signify. When Fares is forbidden to participate, Mara'ana shows how patriarchal structures employ modes of control and oppression, including threats of ostracization, violence and murder (under the guise of honor killings) to enforce women's submission. As a public and political figure, who has used her own positionality as a Palestinian woman and Israeli citizen to criticize both Israeli authorities and the treatment of women in Arab society, Mara'ana is implicated in the film. This connection is further cemented when she becomes the family's spokesperson three years after the release of the documentary when Fare's sister Jamila (known as Maya) is killed. This article explores the overlapping conflicts that emerge when a woman from a conservative society participates in a pageant and the particular situation of a Druze woman in Israel as depicted in Mara'ana's documentary.
This paper describes the enhancement of the rate of hole transfer from a photoexcited CdS quantum dot (QD), with radius R = 2.0 nm, to a molecular acceptor, phenothiazine (PTZ), by linking the donor ...and acceptor through a phenyldithiocarbamate (PTC) linker, which is known to lower the confinement energy of the excitonic hole. Upon adsorption of PTC, the bandgap of the QD decreases due to delocalization of the exciton, primarily the excitonic hole, into interfacial states of mixed QD/PTC character. This delocalization enables hole transfer from the QD to PTZ in <300 fs (within the instrument response of the laser system) when linked by PTC, but not when linked by a benzoate group, which has a similar length and conjugation as PTC but does not delocalize the excitonic hole. Comparison of the two systems was aided by quantification of the surface coverage of benzoate and PTC-linked PTZ by 1H NMR. This work provides direct spectroscopic evidence of the enhancement of the rate of hole extraction from a colloidal QD through covalent linkage of a hole acceptor through an exciton-delocalizing ligand.
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