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Drug air pollution & Eco friendly Growth Goals.
s atomic structure can undergo phase transformations while the other composition remains intact. For length scales, we show how the chemically induced transformations greatly differ between bulk, nanocrystal, and nanocluster characteristic sizes. For instance, the structural transformation on relatively large nanocrystals (2-100 nm) can be a continuous process when the activation volume is smaller than the nanocrystal, while for smaller nanoclusters ( less then 2 nm) the transformation kinetics could be swift resulting in only discrete thermodynamic states. Comparing the two nanosystems (nanocrystals to small nanoclusters), we address how their atomic structural differences can direct the divergent transformation phenomena and the corresponding mechanisms. Understanding the nanoscale mechanisms of chemically induced transformations and how they differ from bulk processes is key to unlocking new science and for implementing this processing for functional materials.As the global threat of plastic pollution has grown in scale and urgency, so have efforts to find sustainable and efficient solutions. Research conducted over the past few years has identified gut environments within insect larvae, including Tenebrio molitor (yellow mealworms), as microenvironments uniquely suited to rapid plastic biodegradation. However, there is currently limited understanding of how the insect host and its gut microbiome collaborate to create an environment conducive to plastic biodegradation. In this work, we provide evidence that T. molitor secretes one or more emulsifying factor(s) (30-100 kDa) that mediate plastic bioavailability. We also demonstrate that the insect gut microbiome secretes factor(s) ( less then 30 kDa) that enhance respiration on polystyrene (PS). We apply these insights to culture PS-fed gut microbiome enrichments, with elevated rates of respiration and degradation compared to the unenriched gut microbiome. Within the enrichment, we identified eight unique gut microorganisms associated with PS biodegradation including Citrobacter freundii, Serratia marcescens, and Klebsiella aerogenes. Our results demonstrate that both the mealworm itself and its gut microbiome contribute to accelerated plastic biodegradation. This work provides new insights into insect-mediated mechanisms of plastic degradation and potential strategies for cultivation of plastic-degrading microorganisms in future investigations and scale-up.Pore size and functionalization are two critical factors for covalent organic frameworks (COFs) as effective adsorbents. However, due to the low crystallinity of COFs, it is a grand challenge to accomplish pore diameter adjustment and functionalization at the same time. In this work, we developed a simple and ingenious strategy, cutting off linkage, to synchronously construct hierarchical porosity and modify thiol groups in COFs under mild conditions. The hybrid COFs containing disulfide bonds were designed and synthesized, and then the disulfide bonds were cleaved by glutathione, resulting in the formation of thiol groups as well as the increase in pore size caused by skeleton defects. ReACp53 molecular weight The pore diameter of thiol-functionalized hierarchical porous COFs (denoted as HP-TpEDA-SH) was concentrated at 2.6 and 3.5 nm. Thanks to the electrostatic attraction of thiol groups to cationic dyes and the higher number of available adsorption sites, the maximum extraction amounts of methylene blue (MB), malachite green (MG), and crystal violet (CV) by HP-TpEDA-SH were 2.6, 2.1, and 3.3 times those of microporous COFs under optimal extraction conditions, respectively. The proposed analytical method (solid-phase extraction-high-performance liquid chromatography/ultraviolet (SPE-HPLC/UV)) with HP-TpEDA-SH as the adsorbent showed low detection limits of 1.3, 0.13, and 0.12 μg·L-1 for MB, MG, and CV, respectively. The recoveries of three spiked water samples ranged from 81.5 to 113.8%, with relative standard deviations (RSDs) less than 9.7%. This work not only opened a new avenue for the preparation of functionalized hierarchical porous COFs but also established an effective method for detecting trace cationic dyes in fishery water.The novel photosensitizer [Ru(S-Sbpy)(bpy)2]2+ harbors two distinct sets of excited states in the UV/Vis region of the absorption spectrum located on either bpy or S-Sbpy ligands. Here, we address the question of whether following excitation into these two types of states could lead to the formation of different long-lived excited states from where energy transfer to a reactive species could occur. Femtosecond transient absorption spectroscopy identifies the formation of the final state within 80 fs for both excitation wavelengths. The recorded spectra hint at very similar dynamics following excitation toward either the parent or sulfur-decorated bpy ligands, indicating ultrafast interconversion into a unique excited-state species regardless of the initial state. Non-adiabatic surface hopping dynamics simulations show that ultrafast spin-orbit-mediated mixing of the states within less than 50 fs strongly increases the localization of the excited electron at the S-Sbpy ligand. Extensive structural relaxation within this sulfurated ligand is possible, via S-S bond cleavage that results in triplet state energies that are lower than those in the analogue [Ru(bpy)3]2+. This structural relaxation upon localization of the charge on S-Sbpy is found to be the reason for the formation of a single long-lived species independent of the excitation wavelength.Solid-gas-water phase partitioning of mercury (Hg) and the processes governing its diffusivity within soils are poorly studied. In this study, landscape and forest species dependences of gaseous elemental Hg (Hg(0)) in soil profiles (0-50 cm) were investigated over four seasons in eight subtropical (130 days) and temperate (96 days) forest plots. The vertical soil pore Hg(0) concentrations differed between subtropical (Masson pine, broad-leaved forest, and open field) and temperate (Chinese pine, larch, mixed broad-leaf forests, and open field) catchments, with annual averages ranging from 6.73 to 15.8 and 0.95 to 2.08 ng m-3, respectively. The highest Hg(0) concentrations in soil gas consistently occurred in the upper mineral or organic horizons, indicating immobilization of Hg(0) in mineral soils. A strongly positive relationship between pore Hg(0) concentrations and ratios of Hg to organic matter (SOM) in soils suggests that the vertical distribution of Hg(0) is related to soil Hg(0) formation by Hg(II) reduction and sorption to SOM.
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