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ABSTRACT Ecosystems are abruptly changing due to invasive species and global climate change. In lakes, invasive Rainbow Smelt Osmerus mordax can cause negative ecosystem effects through competitive and predatory interactions with native species leading to food web shifts away from native species dominance, altered zooplankton communities, and the decline or extirpation of native cool and coldwater fishes. We conducted two whole-lake removals of invasive Rainbow Smelt and simultaneous introductions of native Cisco Coregonus artedi through stocking. About 327 and 1.6 adult Rainbow Smelt/ha were removed and about 45 adult Cisco/ha were stocked over 4 years into the two experimental lakes. In one system, native Yellow Perch Perca flavscens relative abundance and density significantly increased by 556% and 143% post-manipulation, respectively. In the other system, native Walleye Sander vitreus relative abundance increased by 26% and became consistently present in the pelagic zone post-manipulation (allowing for density estimation). Rainbow Smelt relative abundance and density decreased by >85% in both experimental lakes. The two ecosystems shifted to native species dominance while invasive Rainbow Smelt became insignificant components of the food webs. In these two intensive whole-lake manipulations, we applied the Resist–Accept–Direct (RAD) climate adaptation framework to test an applicable ecological adaptation strategy and used panarchy theory as an ecologically grounded pathway to purposefully direct ecosystem transformation. We used this holistic management framework to better understand and manage undesired ecological change—“food web thinking.” In the context of our study, two ecosystems were purposefully directed towards native food web structures, species interactions, and processes, which mitigated Rainbow Smelt driven negative effects. 

ArticleSize-Controlled Synthesis of Rhodium Nanocatalysts and Applications in Low-Temperature HydroformylationAndrew Lamkins 1,2, Charles J. Ward 1,2, Jeffrey T. Miller 3, Ziad Alsudairy 4, Xinle Li 4, Joseph Thuma 1,2, Ruoyu Cui 1,2, Xun Wu 1,2, Levi M. Stanley 1 and Wenyu Huang 1,2,*1 Department of Chemistry, Iowa State University, Ames, IA 50010, USA2 Ames Laboratory, U.S. Department of Energy, Ames, IA 50010, USA3 Davidson School of Chemical Engineering, Purdue University, West Lafayette, IN 47907, USA4 Department of Chemistry, Clark Atlanta University, Atlanta, GA 30314, USA* Correspondence: whuang@iastate.eduReceived: 3 December 2024; Revised: 30 December 2024; Accepted: 3 January 2025; Published: 10 January 2025 Abstract: Controlling the size and distribution of metal nanoparticles is one of the simplest methods of tuning the catalytic properties of a material. For a nanocrystal particle, the ratio of edge-to-terrace sites can be critical in determining its catalytic activity and selectivity to desired products. To study these effects, we have developed a simple impregnation method of controlling the dispersion of rhodium atoms at the same metal loading in the range of nanoparticles less than 10 nm. Rh precursor salts are loaded onto inert SBA-15, and increasing the ratio of chloride to acetylacetonate salts improves the dispersion of rhodium atoms to form small Rh nanoparticles. Extensive characterization of the size-controlled catalysts, including XAS and in-situ CO-DRIFTS studies, has been performed to characterize the structure of Rh nanoparticles. Applying these catalysts to the hydroformylation of styrene, we observed that turnover frequency increases with decreasing particle size from 6.4 to 1.6 nm. When applied to hydroformylation reactions, we achieved a high branched product selectivity and successfully demonstrated a route to synthesizing the pain relief drug ibuprofen. This simple method can also synthesize Pt and Pd nanoparticles between 2–10 nm. 

Abstract We measure the projected two-point correlation functions of emission-line galaxies (ELGs) from the Dark Energy Spectroscopic Instrument One-Percent Survey and model their dependence on stellar mass and [OII] luminosity. We select ∼180,000 ELGs with redshifts of 0.8 < z < 1.6, and define 27 samples according to cuts in redshift and both galaxy properties. Following a framework that describes the conditional [OII] luminosity–stellar mass distribution as a function of halo mass, we simultaneously model the clustering measurements of all samples at fixed redshift. Based on the modeling result, most ELGs in our samples are classified as central galaxies, residing in halos of a narrow mass range with a typical median of ∼10^12.2−12.4h⁻¹M_⊙. We observe a weak dependence of clustering amplitude on stellar mass, which is reflected in the model constraints and is likely a consequence of the 0.5 dex measurement uncertainty in the stellar mass estimates. The model shows a trend between galaxy bias and [OII] luminosity at high redshift (1.2 < z < 1.6) that is otherwise absent at lower redshifts. 

Cryogels, known for their biocompatibility and porous structure, lack mechanical strength, while 3D-printed scaffolds have excellent mechanical properties but limited porosity resolution. By combining a 3D-printed plastic gyroid lattice scaffold with a chitosan–gelatin cryogel scaffold, a scaffold can be created that balances the advantages of both fabrication methods. This study compared the pore diameter, swelling potential, mechanical characteristics, and cellular infiltration capability of combined scaffolds and control cryogels. The incorporation of the 3D-printed lattice demonstrated patient-specific geometry capabilities and significantly improved mechanical strength compared to the control cryogel. The combined scaffolds exhibited similar porosity and relative swelling ratio to the control cryogels. However, they had reduced elasticity, reduced absolute swelling capacity, and are potentially cytotoxic, which may affect their performance. This paper presents a novel approach to combine two scaffold types to retain the advantages of each scaffold type while mitigating their shortcomings. 

Direct coupling of unactivated alcohols remains a challenge in synthetic chemistry. Current approaches to cross-coupling of alcohol-derived electrophiles often involve activated alcohols such as tosylates or carbonates. We report the direct arylative substitution of homoallylic alcohols catalyzed by a nickel-bisphosphine complex as a facile method to generate allylic arenes. These reactions proceed via formation of an allylic alcohol intermediate. Subsequent allylic substitution with arylboroxine nucleophiles enables the formation of a variety of allylic arenes. The presence of p -methoxyphenylboronic acid is crucial to activate the allylic alcohol to achieve high product yields. 

We report Ni-catalyzed dearylative cyclocondensation of aldehydes, alkynes, and triphenylborane. The reaction is initiated by oxidative cyclization of the aldehyde and alkyne coupling partners to generate an oxanickelacyclopentene which reacts with triphenylborane to form oxaboranes. This formal dearylative cyclocondensation reaction generates oxaboranes in moderate-to-high yields (47–99%) with high regioselectivities under mild reaction conditions. This approach represents a direct and modular synthesis of oxaboranes which are difficult to access using current methods. These oxaboranes are readily transformed into valuable building blocks for organic synthesis and an additional class of boron heterocycles. Selective homocoupling forms oxaboroles, oxidation generates aldol products, and reduction and arylation form substituted allylic alcohols.