Reducing the size of heterogeneous nanocatalysts is generally conducive to improving their atomic utilization and activities in various catalytic reactions. However, this strategy has proven less ...effective for Cu-based electrocatalysts for the reduction of CO
2
to multicarbon (C
2+
) products, owing to the overly strong binding of intermediates on small-sized (< 15 nm) Cu nanoparticles (NPs). Herein, by incorporating pyrenyl-graphdiyne (Pyr-GDY), we successfully endowed ultrafine (∼ 2 nm) Cu NPs with a significantly elevated selectivity for CO
2
-to-C
2+
conversion. The Pyr-GDY can not only help to relax the overly strong binding between adsorbed H* and CO* intermediates on Cu NPs by tailoring the d-band center of the catalyst, but also stabilize the ultrafine Cu NPs through the high affinity between alkyne moieties and Cu NPs. The resulting Pyr-GDY-Cu composite catalyst gave a Faradic efficiency (FE) for C
2+
products up to 74%, significantly higher than those of support-free Cu NPs (C
2+
FE, ~ 2%), carbon nanotube-supported Cu NPs (CNT-Cu, C
2+
FE, ~ 18%), graphene oxide-supported Cu NPs (GO-Cu, C
2+
FE, ~ 8%), and other reported ultrafine Cu NPs. Our results demonstrate the critical influence of graphdiyne on the selectivity of Cu-catalyzed CO
2
electroreduction, and showcase the prospect for ultrafine Cu NPs catalysts to convert CO
2
into value-added C
2+
products.
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•Plate-shaped CoMn2O4 was synthesized using MOFs as precursor.•The catalyst showed large specific surface area and abundant active sites.•It had much higher catalytic activity than ...previously-reported CoMn2O4 catalyst.•The Co-Mn synergy in heterogeneous catalysis were elucidated.•The material showed good stability and reusability for SA removal.
Spinel-type CoMn2O4 materials are promising catalyst for heterogeneous activation of peroxymonosulfate (PMS), but the catalytic activity still need considerable improvements for practical environmental application and the underlying Co-Mn synergy is unclear. In this work, we synthesized CoMn2O4 microplates by using CoMn2-perylene-3,4,9,10-tetracarboxylic dianhydride (ptcda) metal organic frameworks (MOFs) as the precursor. The resulting material showed significantly higher catalytic activity for the PMS activation and sulfanilamide (SA) degradation than the CoMn2O4 obtained by conventional solvothermal synthesis methods, due to its much higher specific surface area and abundant surface hydroxyl groups as the active sites. In addition, the Co-Mn synergy in the synthesized material for the efficient heterogeneous catalysis was elucidated. The catalyst stability was also evaluated. Our work may lay the foundation for optimized design of highly-efficient heterogeneous catalyst for environmental application.
Canola (Brassica napus) is a widely cultivated species and provides important resources of edible vegetable oil, biodiesel production and animal feed. Seed development in Arabidopsis and canola ...shares a similar path: an early proliferation of endosperm to form a large seed cavity, followed by a second phase in which the embryo grows to replace the endosperm. In Arabidopsis, the seed reaches almost its final volume before the enlargement of the embryo. SHORT HYPOCOTYL UNDER BLUE1 (SHB1) is a key regulatory gene of seed development with a broad expression beyond endosperm development. By contrast, its two target genes, MINISEED3 (MINI3) and HAIKU2 (IKU2), are narrowly expressed in early developing endosperm and early embryo. We overexpressed SHB1 in canola to explore the possibility of altering seed development. As an alternative strategy, we expressed the canola IKU2 ortholog in Arabidopsis endosperm under the control of a stronger MINI3 promoter. SHB1 targeted canola orthologs of Arabidopsis MINI3 and IKU2 and caused a significantly increased seed mass. Overaccumulation of IKU2 in the early stage of Arabidopsis seed development also significantly increased the final seed mass. Our studies provide a strong case for increasing the final seed mass by manipulating endosperm proliferation at a rather early developmental stage in crops.
Population increase and migration from rural areas to urbanized regions have resulted in the formation of gray cities mainly comprised of impervious surfaces. High quantities of stormwater runoff ...containing pollutants from gray cities cause problems including inland flooding and water pollution. An innovative and evolving response to this global issue is the development of green cities that utilize low impact development (LID) and analogous initiatives. This paper aims to assess LID efforts and relevant governmental policies from a global perspective. It provides a vantage on major evolving LID technologies, where the best policies regarding planning, design, construction, and management are still not well known. The case studies of LID and relevant governmental policies around the world are presented to facilitate future quantitative and qualitative stormwater management in urban regions. This study found that the western and eastern regions around the globe have different driving forces and attitudes regarding implementing LID. These differences are reflected in the name of their LID-like initiatives with varying ramifications. The western regions, such as the United States, pay more attention to restoring water quality, whereas the eastern regions, such as China, prioritize flood prevention and rainwater harvesting. Levying stormwater fees and indirect subsidies by offering a discount are effective for promoting LID to some extent. This paper also provides an in-depth discussion in regard to the latest essence of LID technologies, which magnify their ability to manage stormwater while also providing societal, environmental, hydrological, and aesthetic benefits. Governments should encourage and support the development of green cities by using LID and analogous initiatives.
Nod-like receptor protein 3 (NLRP3)-associated neuroinflammation mediated by activated microglia is involved in the pathogenesis of depression. The role of the pore-forming protein gasdermin D ...(GSDMD), a newly identified pyroptosis executioner downstream of NLRP3 inflammasome mediating inflammatory programmed cell death, in depression has not been well defined. Here, we provide evidence that paeoniflorin (PF), a monoterpene glycoside compound derived from
Paeonia lactiflora
, ameliorated reserpine-induced mouse depression-like behaviors, characterized as increased mobility time in tail suspension test and forced swimming test, as well as the abnormal alteration of synaptic plasticity in the depressive hippocampus. The molecular docking simulation predicted that PF would interact with C-terminus of GSDMD. We further demonstrated that PF administration inhibited the enhanced expression of GSDMD which mainly distributed in microglia, along with the proteins involved in pyroptosis signaling transduction including caspase (CASP)-11, CASP-1, NLRP3, and interleukin (IL)-1β in the hippocampus of mice treated with reserpine. And also, PF prevented lipopolysaccharide (LPS) and adenosine triphosphate (ATP)-induced pyroptosis in murine N9 microglia in vitro, evidenced by inhibiting the expression of CASP-11, NLRP3, CASP-1 cleavage, as well as IL-1β. Furthermore, VX-765, an effective and selective inhibitor for CASP-1 activation, reduced the expression of inflammasome and pyroptosis-associated proteins in over-activated N9 and also facilitated PF-mediated inhibition of pyroptosis synergistically. Collectively, the data indicated that PF exerted antidepressant effects, alleviating neuroinflammation through inhibiting CASP-11-dependent pyroptosis signaling transduction induced by over-activated microglia in the hippocampus of mice treated with reserpine. Thus, GSDMD-mediated pyroptosis in activated microglia is a previously unrecognized inflammatory mechanism of depression and represents a unique therapeutic opportunity for mitigating depression given PF administration.
•Sustainability patterns in an urban agriculture network are critical for urban systems analysis.•Comparison relative to benchmark supports scaling up the urban agriculture network.•Clustering ...analysis of the urban agriculture sites helps identify the priority for governance.•Multicriteria decision making can prioritize scenarios for better governance.
Environmental, social, and economic sustainability patterns interact in various dimensions of an urban environment. Exacerbated population growth triggers an emphasis on better resource management strategies addressing the balance of supply and demand over food, energy, and water sectors while considering social and economic development. Promoting sustainable development goals requires governance structures and functions within and across the food, energy, and water sectors, specifically due to polycentric urban development. This study emphasizes food security via an urban agriculture network in the greater Miami metropolitan area, encompassing the three counties of Palm-Beach, Broward, and Miami-Dade. Given the existing governance structure, we quantified several sustainability indices for clustering analysis to agglomerate urban agricultural sites (UASs) and to help identify the priority of clusters in terms of vulnerability or risk level according to their priority index in multicriteria decision-making. The cases of eight clusters were selected for the visualization of the UASs ranked by multicriteria decision-making based on scenarios prioritized for governance under the impacts of climate change, social equity, and economic development. The role of governance structure was highlighted for signifying the incentive programs to enhance the overall sustainability performance of UASs in an urban food–energy–water nexus.
There is an urgent need to identify biomarkers of early response that can accurately predict the benefit of immune checkpoint inhibitors (ICI). Patients receiving durvalumab/tremelimumab had tumor ...samples sequenced before treatment (baseline) to identify variants for the design of a personalized circulating tumor (ctDNA) assay. ctDNA was assessed at baseline and at 4 and/or 8 weeks into treatment. Correlations between ctDNA changes to radiographic response and overall survival (OS) were made to assess potential clinical benefit. 35/40 patients (87.5%) had personalized ctDNA assays designed, and 29/35 (82.9%) had plasma available for baseline analysis, representing 16 unique solid tumor histologies. As early as 4 weeks after treatment, decline in ctDNA from baseline predicted improved OS (P = 0.0144; HR = 9.98) and ctDNA changes on treatment‐supported and refined radiographic response calls. ctDNA clearance at any time through week 8 identified complete responders by a median lead time of 11.5 months ahead of radiographic imaging. ctDNA response monitoring is emerging as a dynamic, personalized biomarker method that may predict survival outcomes in patients with diverse solid tumor histologies, complementing and sometimes preceding standard‐of‐care imaging assessments.
We used a novel approach combining a tissue‐informed comprehensive genomic profiling assay with personalized blood‐based monitoring demonstrating that early ctDNA dynamics predict long‐term clinical outcomes in patients with different solid tumors treated with immune checkpoint inhibition. Molecular response as measured by ctDNA change from baseline represents an important emerging tool for assessing drug effect, complementary to imaging‐based response assessment.
This study systematically reviewed the performance of bandage contact lenses (BCL) such as lotrafilcon A, lotrafilcon B, senofilcon A, balafilcon A, and comfilcon A as postoperative treatment in ...different ocular surgeries. A systematic search of English and Chinese databases (from inception to December 2021) was conducted for studies reporting the efficacy of BCLs after ocular surgeries. Postoperative symptoms, corneal healing, and visual outcomes were studied. Overall, 38 studies were identified. Bandage contact lens was applied as a postoperative aid in corneal refractive, cataract, and vitrectomy surgeries. Most studies were on photorefractive keratectomy. Reduced postoperative symptoms were observed within 4 hr to 3 days, whereas re-epithelization of the cornea and healing was complete within 3 to 7 days after ocular surgeries except for vitrectomy. In a vitrectomy, greater comfort and improved corneal epithelium were observed on the seventh day after surgery. An improvement in dry eye symptoms was observed at 7 days with considerable benefits observed after 1 month of cataract surgery. These findings indicate that BCLs are effective for improving postoperative symptoms and facilitation of early visual rehabilitation with a wear time of 8 hr to 7 days depending on the type of ocular surgery.
An efficient palladium-catalyzed asymmetric hydrogenation of a variety of unprotected indoles has been developed that gives up to 98% ee using a strong Brønsted acid as the activator. This ...methodology was applied in the facile synthesis of biologically active products containing a chiral indoline skeleton. The mechanism of Pd-catalyzed asymmetric hydrogenation was investigated as well. Isotope-labeling reactions and ESI-HRMS proved that an iminium salt formed by protonation of the CC bond of indoles was the significant intermediate in this reaction. The important proposed active catalytic Pd–H species was observed with 1H NMR spectroscopy. It was found that proton exchange between the Pd–H active species and solvent trifluoroethanol (TFE) did not occur, although this proton exchange had been previously observed between metal hydrides and alcoholic solvents. Density functional theory calculations were also carried out to give further insight into the mechanism of Pd-catalyzed asymmetric hydrogenation of indoles. This combination of experimental and theoretical studies suggests that Pd-catalyzed hydrogenation goes through a stepwise outer-sphere and ionic hydrogenation mechanism. The activation of hydrogen gas is a heterolytic process assisted by trifluoroacetate of Pd complex via a six-membered-ring transition state. The reaction proceeds well in polar solvent TFE owing to its ability to stabilize the ionic intermediates in the Pd–H generation step. The strong Brønsted acid activator can remarkably decrease the energy barrier for both Pd–H generation and hydrogenation. The high enantioselectivity arises from a hydrogen-bonding interaction between N–H of the iminium salt and oxygen of the coordinated trifluoroacetate in the eight-membered-ring transition state for hydride transfer, while the active chiral Pd complex is a typical bifunctional catalyst, effecting both the hydrogenation and hydrogen-bonding interaction between the iminium salt and the coordinated trifluoroacetate of Pd complex. Notably, the Pd-catalyzed asymmetric hydrogenation is relatively tolerant to oxygen, acid, and water.
For comprehensive flood assessment, complex systems, both natural and man-made, must be accounted for due to prevailing cascade effects from the upper atmosphere to the subsurface with hydrological ...and hydraulic interactions in between. This study aims to demonstrate such cascade effects via an integrated nearshore oceanic and coastal watershed model. Such an integrated modeling system consists of a coupled hydrodynamic circulation and wave driven model the ADvanced CIRCulation (ADCIRC) and Simulating WAves Nearshore (SWAN) models, which can combine storm surge, astronomic tide levels and wave interaction, as well as an integrated hydrological/hydraulic model, namely the Interconnected Channel and Pond Routing (ICPR) model for coastal urban watershed simulation. In order to explore the worst scenario of coastal flooding impacts on a low-lying coastal watershed, the Cross Bayou Watershed within the Tampa Bay area of Florida was chosen for a multi-scale simulation analysis. To assess hurricane-induced storm tide, precipitation variability, and sea level rise collectively this multi-scale simulation analysis combines ADCIRC/SWAN and ICPR integratively. Findings indicate that such consideration of complex interactions at the coastal ocean, land surface, and sub-surface levels can provide useful flood assessments which are sensitive to slight changes in natural hazard characteristics such as storm intensity, radius of maximum winds, storm track, and landfall location.
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