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1. Esters as Radical Acceptors: β‐NHC‐Borylalkenyl Radicals Induce Lactonization by C−C Bond Formation/Cleavage on Esters

   https://doi.org/10.1002/anie.201902001  

   Shimoi, Masaki; Maeda, Katsuhiro; Geib, Steven J.; Curran, Dennis P.; Taniguchi, Tsuyoshi (April 2019, Angewandte Chemie International Edition)

   Abstract Substituted propargyl acetates are converted into 4‐boryl‐2(5H)‐furanones upon thermolysis in the presence of an N‐heterocyclic carbene borane (NHC‐borane) and di‐tert‐butyl peroxide. The acetyl methyl group is lost during the reaction as methane. Evidence suggests that the reaction proceeds by a sequence of radical events including: 1) addition of an NHC‐boryl radical to the triple bond; 2) cyclization of the resultant β‐borylalkenyl radical to the ester carbonyl group; 3) β‐scission of the so‐formed alkoxy radical to provide the 4‐boryl‐2(5H)‐furanone and a methyl radical; and 4) hydrogen abstraction from the NHC‐borane to return the initial NHC‐boryl radical and methane. 

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2. Low-frequency Radio Recombination Lines Away from the Inner Galactic Plane

   https://doi.org/10.3847/1538-3881/ad08ba  

   Vydula, Akshatha K.; Bowman, Judd D.; Lewis, David; Crawford, Kelsie; Kolopanis, Matthew; Rogers, Alan E. E.; Murray, Steven G.; Mahesh, Nivedita; Monsalve, Raul A.; Sims, Peter; et al (December 2023, The Astronomical Journal)

   Abstract Diffuse radio recombination lines (RRLs) in the Galaxy are possible foregrounds for redshifted 21 cm experiments. We use EDGES drift scans centered at −26.°7 decl. to characterize diffuse RRLs across the southern sky. We find that RRLs averaged over the large antenna beam (72° × 110°) reach minimum amplitudes of R.A. = 2–6 hr. In this region, the Cαabsorption amplitude is 33 ± 11 mK (1σ) averaged over 50–87 MHz (27 ≳z≳ 15 for the 21 cm line) and increases strongly as frequency decreases. Cβand Hαlines are consistent with no detection with amplitudes of 13 ± 14 and 12 ± 10 mK (1σ), respectively. At 108–124.5 MHz (z≈ 11) in the same region, we find no evidence for carbon or hydrogen lines at the noise level of 3.4 mK (1σ). Conservatively assuming that observed lines come broadly from the diffuse interstellar medium, as opposed to a few compact regions, these amplitudes provide upper limits on the intrinsic diffuse lines. The observations support expectations that Galactic RRLs can be neglected as significant foregrounds for a large region of sky until redshifted 21 cm experiments, particularly those targeting cosmic dawn, move beyond the detection phase. We fit models of the spectral dependence of the lines averaged over the large beam of EDGES, which may contain multiple line sources with possible line blending, and find that including degrees of freedom for expected smooth, frequency-dependent deviations from local thermodynamic equilibrium (LTE) is preferred over simple LTE assumptions for Cαand Hαlines. For Cαwe estimate departure coefficients 0.79 <b_nβ_n< 4.5 along the inner Galactic plane and 0 <b_nβ_n< 2.3 away from the inner Galactic plane. 

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3. Towards a Schinzel–Wójcik theorem for number fields

   https://doi.org/10.1007/s40879-025-00819-8  

   Pollack, Paul (April 2025, European Journal of Mathematics)

   Abstract Schinzel and Wójcik have shown that for every$$\alpha ,\beta \in \mathbb {Q}^{\times }\hspace{0.55542pt}{\setminus }\hspace{1.111pt}\{\pm 1\}$$ $\alpha ,\beta \in Q^{\times }\backslash \{\pm 1\}$, there are infinitely many primespwhere$$v_p(\alpha )=v_p(\beta )=0$$ $v_p\left(\alpha \right)=v_p\left(\beta \right)=0$and where$$\alpha $$ $\alpha$and$$\beta $$ $\beta$generate the same multiplicative group modp. We prove a weaker result in the same direction for algebraic numbers$$\alpha , \beta $$ $\alpha ,\beta$. Let$$\alpha , \beta \in \overline{\mathbb {Q}} ^{\times }$$ $\alpha ,\beta \in {\overline{Q}}^{\times }$, and suppose$$|N_{\mathbb {Q}(\alpha ,\beta )/\mathbb {Q}}(\alpha )|\ne 1$$ $|N_{Q(\alpha ,\beta )/Q}\left(\alpha \right)|\ne 1$and$$|N_{\mathbb {Q}(\alpha ,\beta )/\mathbb {Q}}(\beta )|\ne 1$$ $|N_{Q(\alpha ,\beta )/Q}\left(\beta \right)|\ne 1$. Then for some positive integer$$C = C(\alpha ,\beta )$$ $C=C(\alpha ,\beta )$, there are infinitely many prime idealsPof Equation missing<#comment/>where$$v_P(\alpha )=v_P(\beta )=0$$ $v_P\left(\alpha \right)=v_P\left(\beta \right)=0$and where the group$$\langle \beta \bmod {P}\rangle $$ $⟨\beta modP⟩$is a subgroup of$$\langle \alpha \bmod {P}\rangle $$ $⟨\alpha modP⟩$with$$[\langle \alpha \bmod {P}\rangle \,{:}\, \langle \beta \bmod {P}\rangle ]$$ $[⟨\alpha modP⟩:⟨\beta modP⟩]$dividingC. A key component of the proof is a theorem of Corvaja and Zannier bounding the greatest common divisor of shiftedS-units. 

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4. JWST/NIRSpec Measurements of Extremely Low Metallicities in High Equivalent Width Lyα Emitters

   https://doi.org/10.3847/1538-4357/acf12b  

   Maseda, Michael_V; Lewis, Zach; Matthee, Jorryt; Hennawi, Joseph_F; Boogaard, Leindert; Feltre, Anna; Nanayakkara, Themiya; Bacon, Roland; Barger, Amy; Brinchmann, Jarle; et al (October 2023, The Astrophysical Journal)

   Abstract Deep Very Large Telescope/MUSE optical integral field spectroscopy has recently revealed an abundant population of ultra-faint galaxies (M_UV≈ −15; 0.01L_⋆) atz= 2.9−6.7 due to their strong Lyαemission with no detectable continuum. The implied Lyαequivalent widths can be in excess of 100–200 Å, challenging existing models of normal star formation and indicating extremely young ages, small stellar masses, and a very low amount of metal enrichment. We use JWST/NIRSpec’s microshutter array to follow up 45 of these galaxies (11 hr in G235M/F170LP and 7 hr in G395M/F290LP), as well as 45 lower-equivalent width Lyαemitters. Our spectroscopy covers the range 1.7−5.1 micron in order to target strong optical emission lines: Hα, [Oiii], Hβ, and [N II]. Individual measurements as well as stacks reveal line ratios consistent with a metal-poor nature (2%−40%Z_⊙, depending on the calibration). The galaxies with the highest equivalent widths of Lyα, in excess of 90 Å, have lower [N II]/Hα(1.9σ) and [Oiii]/Hβ(2.2σ) ratios than those with lower equivalent widths, implying lower gas-phase metallicities at a combined significance of 2.4σ. This implies a selection based on Lyαequivalent width is an efficient technique for identifying younger, less chemically enriched systems. 

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5. Helical twists and β‐turns in structures at serine–proline sequences: Stabilization of cis ‐proline and type VI β‐turns via C–H/O interactions

   https://doi.org/10.1002/prot.26701  

   Oven, Harrison_C; Yap, Glenn_P_A; Zondlo, Neal_J (May 2024, Proteins: Structure, Function, and Bioinformatics)

   Abstract Structures at serine‐proline sites in proteins were analyzed using a combination of peptide synthesis with structural methods and bioinformatics analysis of the PDB. Dipeptides were synthesized with the proline derivative (2S,4S)‐(4‐iodophenyl)hydroxyproline [hyp(4‐I‐Ph)]. The crystal structure of Boc‐Ser‐hyp(4‐I‐Ph)‐OMe had two molecules in the unit cell. One molecule exhibitedcis‐proline and a type VIa2 β‐turn (BcisD). Thecis‐proline conformation was stabilized by a C–H/O interaction between Pro C–H_αand the Ser side‐chain oxygen. NMR data were consistent with stabilization ofcis‐proline by a C–H/O interaction in solution. The other crystallographically observed molecule hadtrans‐Pro and both residues in the PPII conformation. Two conformations were observed in the crystal structure of Ac‐Ser‐hyp(4‐I‐Ph)‐OMe, with Ser adopting PPII in one and the β conformation in the other, each with Pro in the δ conformation andtrans‐Pro. Structures at Ser‐Pro sequences were further examined via bioinformatics analysis of the PDB and via DFT calculations. Ser‐Pro versus Ala–Pro sequences were compared to identify bases for Ser stabilization of local structures. C–H/O interactions between the Ser side‐chain O_γand Pro C–H_αwere observed in 45% of structures with Ser‐cis‐Pro in the PDB, with nearly all Ser‐cis‐Pro structures adopting a type VI β‐turn. 53% of Ser‐trans‐Pro sequences exhibited main‐chain CO_i•••HN_i+3or CO_i•••HN_i+4hydrogen bonds, with Ser as theiresidue and Pro as thei + 1 residue. These structures were overwhelmingly either type I β‐turns or N‐terminal capping motifs on α‐helices or 3₁₀‐helices. These results indicate that Ser‐Pro sequences are particularly potent in favoring these structures. In each, Ser is in either the PPII or β conformation, with the Ser O_γcapable of engaging in a hydrogen bond with the amide N–H of thei + 2 (type I β‐turn or 3₁₀‐helix; Serχ₁t) ori + 3 (α‐helix; Serχ₁g⁺) residue. Non‐prolinecisamide bonds can also be stabilized by C–H/O interactions. 

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