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1. Migratory functionalization of unactivated alkyl bromides for construction of all-carbon quaternary centers via transposed tert-C-radicals

   https://doi.org/10.1038/s41467-020-18658-4  

   Zhu, Chuan ; Liu, Ze-Yao ; Tang, Luning ; Zhang, Heng ; Zhang, Yu-Feng ; Walsh, Patrick J. ; Feng, Chao ( December 2020 , Nature Communications)

   null (Ed.)

   Abstract Despite remarkable recent advances in transition-metal-catalyzed C(sp 3 )−C cross-coupling reactions, there remain challenging bond formations. One class of such reactions include the formation of tertiary -C(sp 3 )−C bonds, presumably due to unfavorable steric interactions and competing isomerizations of tertiary alkyl metal intermediates. Reported herein is a Ni-catalyzed migratory 3,3-difluoroallylation of unactivated alkyl bromides at remote tertiary centers. This approach enables the facile construction of otherwise difficult to prepare all-carbon quaternary centers. Key to the success of this transformation is an unusual remote functionalization via chain walking to the most sterically hindered tertiary C(sp 3 ) center of the substrate. Preliminary mechanistic and radical trapping studies with primary alkyl bromides suggest a unique mode of tertiary C-radical generation through chain-walking followed by Ni–C bond homolysis. This strategy is complementary to the existing coupling protocols with tert -alkyl organometallic or -alkyl halide reagents, and it enables the expedient formation of quaternary centers from easily available starting materials. 

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2. The RESOLVE and ECO Gas in Galaxy Groups Initiative: The Group Finder and the Group H i–Halo Mass Relation

   https://doi.org/10.3847/1538-4357/acefd4  

   Hutchens, Zackary L. ; Kannappan, Sheila J. ; Berlind, Andreas A. ; Asad, Mehnaaz ; Eckert, Kathleen D. ; Stark, David V. ; Carr, Derrick S. ; Castelloe, Ella R. ; Baker, Andrew J. ; Hess, Kelley M. ; et al ( October 2023 , The Astrophysical Journal)

   We present a four-step group-finding algorithm for the Gas in Galaxy Groups (G3) initiative, a spin-off of thez∼ 0 REsolved Spectroscopy Of a Local VolumE (RESOLVE) and Environmental COntext (ECO) surveys. In preparation for future comparisons to intermediate redshift (e.g., the LADUMA survey), we design the group finder to adapt to incomplete, shallow, or nonuniform data. We use mock catalogs to optimize the group finder’s performance. Compared to friends-of-friends (with false-pair splitting), the G3 algorithm offers improved completeness and halo-mass recovery with minimal loss of purity. Combining it with the volume-limited Hicensus data for RESOLVE and ECO, we examine the Hicontent of galaxy groups as a function of group halo mass. Group-integrated HimassM_{H I,grp}rises monotonically over halo massesM_halo∼ 10¹¹–10^14.5M_⊙, pivoting in slope atM_halo∼ 10^11.4M_⊙, the gas-richness threshold scale. We present the first measurement of the scatter in this relation, which has a median of ∼0.3 dex and is asymmetric toward lowerM_{H I,grp}. We discuss interesting tensions with theoretical predictions and prior measurements of theM_{H I,grp}–M_halorelation. In an appendix, we release RESOLVE DR4 and ECO DR3, including updates to survey redshifts, photometry, and group catalogs, as well as a major expansion of the ECO Hiinventory with value-added data products.

    

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3. Self‐Driven Multistep Quantum Dot Synthesis Enabled by Autonomous Robotic Experimentation in Flow

   https://doi.org/10.1002/aisy.202000245  

   Abdel-Latif, Kameel ; Epps, Robert W. ; Bateni, Fazel ; Han, Suyong ; Reyes, Kristofer G. ; Abolhasani, Milad ( December 2020 , Advanced Intelligent Systems)

   Identifying the optimal formulation of emerging inorganic lead halide perovskite quantum dots (LHP QDs) with their vast colloidal synthesis universe and multiple synthesis/postsynthesis processing parameters is a challenging undertaking for material‐ and time‐intensive, batch synthesis strategies. Herein, a modular microfluidic synthesis strategy, integrated with an artificial intelligence (AI)‐guided decision‐making agent for intelligent navigation through the complex colloidal synthesis universe of LHP QDs with 10 individually controlled synthesis parameters and an accessible parameter space exceeding 2 × 10⁷, is introduced. Utilizing the developed autonomous microfluidic experimentation strategy within a global learning framework, the optimal formulation of LHP QDs is rapidly identified through a two‐step colloidal synthesis and postsynthesis halide exchange reaction, for 10 different emission colors in less than 40 min per desired peak emission energy. Using two in‐series microfluidic reactors enables continuous bandgap engineering of LHP QDs via in‐line halide exchange reactions without the need for an intermediate washing step. Using an inert gas within a three‐phase flow format enables successful, self‐synchronized continuous delivery of halide salt precursor into moving droplets containing LHP QDs, resulting in accelerated closed‐loop formulation optimization and end‐to‐end continuous manufacturing of LHP QDs with desired optoelectronic properties.

    

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4. The MillenniumTNG Project: refining the one-halo model of red and blue galaxies at different redshifts

   https://doi.org/10.1093/mnras/stad279  

   Hadzhiyska, Boryana ; Hernquist, Lars ; Eisenstein, Daniel ; Delgado, Ana Maria ; Bose, Sownak ; Kannan, Rahul ; Pakmor, Rüdiger ; Springel, Volker ; Contreras, Sergio ; Barrera, Monica ; et al ( July 2023 , Monthly Notices of the Royal Astronomical Society)

   Luminous red galaxies (LRGs) and blue star-forming emission-line galaxies (ELGs) are key tracers of large-scale structure used by cosmological surveys. Theoretical predictions for such data are often done via simplistic models for the galaxy–halo connection. In this work, we use the large, high-fidelity hydrodynamical simulation of the MillenniumTNG project (MTNG) to inform a new phenomenological approach for obtaining an accurate and flexible galaxy-halo model on small scales. Our aim is to study LRGs and ELGs at two distinct epochs, z = 1 and z = 0, and recover their clustering down to very small scales, $r \sim 0.1 \ h^{-1}\, {\rm Mpc}$, i.e. the one-halo regime, while a companion paper extends this to a two-halo model for larger distances. The occupation statistics of ELGs in MTNG inform us that (1) the satellite occupations exhibit a slightly super-Poisson distribution, contrary to commonly made assumptions, and (2) that haloes containing at least one ELG satellite are twice as likely to host a central ELG. We propose simple recipes for modelling these effects, each of which calls for the addition of a single free parameter to simpler halo occupation models. To construct a reliable satellite population model, we explore the LRG and ELG satellite radial and velocity distributions and compare them with those of subhaloes and particles in the simulation. We find that ELGs are anisotropically distributed within haloes, which together with our occupation results provides strong evidence for cooperative galaxy formation (manifesting itself as one-halo galaxy conformity); i.e. galaxies with similar properties form in close proximity to each other. Our refined galaxy-halo model represents a useful improvement of commonly used analysis tools and thus can be of help to increase the constraining power of large-scale structure surveys.

    

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5. An S =1 Iron(IV) Intermediate Revealed in a Non‐Heme Iron Enzyme‐Catalyzed Oxidative C−S Bond Formation

   https://doi.org/10.1002/ange.202309362  

   Paris, Jared C. ; Hu, Sha ; Wen, Aiwen ; Weitz, Andrew C. ; Cheng, Ronghai ; Gee, Leland B. ; Tang, Yijie ; Kim, Hyomin ; Vegas, Arturo ; Chang, Wei‐chen ; et al ( September 2023 , Angewandte Chemie)

   Ergothioneine (ESH) and ovothiol A (OSHA) are two natural thiol‐histidine derivatives. ESH has been implicated as a longevity vitamin and OSHA inhibits the proliferation of hepatocarcinoma. The key biosynthetic step of ESH and OSHA in the aerobic pathways is the O₂‐dependent C−S bond formation catalyzed by non‐heme iron enzymes (e.g., OvoA in ovothiol biosynthesis), but due to the lack of identification of key reactive intermediate the mechanism of this novel reaction is unresolved. In this study, we report the identification and characterization of a kinetically competentS=1 iron(IV) intermediate supported by a four‐histidine ligand environment (three from the protein residues and one from the substrate) in enabling C−S bond formation in OvoA fromMethyloversatilis thermotoleran, which represents the first experimentally observed intermediate spin iron(IV) species in non‐heme iron enzymes. Results reported in this study thus set the stage to further dissect the mechanism of enzymatic oxidative C−S bond formation in the OSHA biosynthesis pathway. They also afford new opportunities to study the structure‐function relationship of high‐valent iron intermediates supported by a histidine rich ligand environment.

    

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