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We demonstrate the ability of a non-heme iron containingl-lysine dioxygenase to perform sequential oxidation on its native substrate and computationally explore structural elements that promote this reactivity. 

We construct a sequence of multisite gates which transform an easily constructed product state into an approx- imation to the superfluid ground state of the Bose-Hubbard model. The mapping is exact in the one-dimensional hard-core limit and for noninteracting particles in both one and two dimensions. The gate sequence has other applications, such as being used as part of a many-body interferometer which probes the existence of doublons. 

van der Waals materials support numerous exotic polaritonic phenomena originating from their layered structures and associated vibrational and electronic properties. However, many van der Waals materials' unique properties are most prominent at cryogenic temperatures. This presents a particular challenge for polaritonics research, as reliable optical constant data are required for understanding light-matter coupling. This paper presents a cryogenic Fourier transform infrared microscope design constructed entirely from off-the-shelf components and associated fitting procedures for determining optical constants in the infrared. Data correction techniques were developed to directly quantify systematic errors in the fitting procedure. We use this microscope to present the first temperature-dependent characterization of the optical properties of hexagonal boron nitride enriched with isotopically pure boron. Our full analysis of the infrared dielectric function shows small but significant tuning of the optical constants, which is highly consistent with Raman data from the literature. We then use this dielectric data to perform and analyze the polariton propagation properties, which agree exceptionally well with published cryogenic scattering-type near-field microscopy results. In addition to the insights gained into hyperbolic polaritons in hBN, our paper represents a transferable framework for characterizing exfoliated infrared polaritonic materials and other infrared devices. This could accelerate discoveries in different material systems, especially those that are spatially inhomogeneous or cannot be prepared as large single crystals. 

Baeyer-Villiger oxidation of alpha-alkoxy ketones 1 provides lactone acetals 2, which react with the lithium salts of di-methyl(alkyl) phosphonates in the presence of LaCl3•2LiCl to provide cyclic enones 3 in good to excellent yields after treatment with dilute aqueous potassium carbonate. Thus, five-, six-, and seven-membered lactones are con-verted to five-, six-, and seven membered cyclic enones. The utility of this two-step ring expansion method is demonstrated in the synthesis of (±)-1-epi-xerantholide from 5-methyl-2-cyclohexen-1-one. 

We examine the microfluidic postprocessing soft colloidal dispersions and reveal a variety of microflow regimes between nanoscale emulsions and solvents. 

Abstract We present 0.6–3.2 pc resolution mid-infrared (MIR) JWST images at 7.7μm (F770W) and 21μm (F2100W) covering the main star-forming regions of two of the closest star-forming low-metallicity dwarf galaxies, NGC 6822 and Wolf–Lundmark–Melotte (WLM). The images of NGC 6822 reveal filaments, edge-brightened bubbles, diffuse emission, and a plethora of point sources. By contrast, most of the MIR emission in WLM is pointlike, with a small amount of extended emission. Compared to solar-metallicity galaxies, the ratio of 7.7μm intensity ( $I_{\nu }^{\mathrm{F770W}}$), tracing polycyclic aromatic hydrocarbons (PAHs), to 21μm intensity ( $I_{\nu }^{\mathrm{F2100W}}$), tracing small, warm dust grain emission, is suppressed in these low-metallicity dwarfs. Using Atacama Large Millimeter/submillimeter Array CO(2–1) observations, we find that detected CO intensity versus $I_{\nu }^{\mathrm{F770W}}$at ≈2 pc resolution in dwarfs follows a similar relationship to that at solar metallicity and lower resolution, while the CO versus $I_{\nu }^{\mathrm{F2100W}}$relationship in dwarfs lies significantly below that derived from solar-metallicity galaxies at lower resolution, suggesting more pronounced destruction of CO molecules at low metallicity. Finally, adding in Local Group L-Band Survey 21 cm Hiobservations from the Very Large Array, we find that $I_{\nu }^{\mathrm{F2100W}}$and $I_{\nu }^{\mathrm{F770W}}$versus total gas ratios are suppressed in NGC 6822 and WLM compared to solar-metallicity galaxies. In agreement with dust models, the level of suppression appears to be at least partly accounted for by the reduced galaxy-averaged dust-to-gas and PAH-to-dust mass ratios in the dwarfs. Remaining differences are likely due to spatial variations in dust model parameters, which should be an exciting direction for future work in local dwarf galaxies. 

Context.The C-19 stellar stream is the most metal-poor stream known to date. While its wth and velocity dispersion indicate a dwarf galaxy origin, its metallicity spread and abundance patterns are more similar to those of globular clusters (GCs). If it is indeed of GC origin, its extremely low metallicity ([Fe/H]=−3.4, estimated from giant stars) implies that these stellar systems can form out of gas that is as extremely poor in metals as this. Previously, only giant stream stars were observed spectroscopically, although the majority of stream stars are unevolved stars. Aims.We pushed the spectroscopic observations to the subgiant branch stars (G≈ 20) in order to consolate the chemical and dynamical properties of C-19. Methods.We used the high-efficiency spectrograph X-shooter fed by the ESO 8.2m VLT telescope to observe 15 candate subgiant C-19 members. The spectra were used to measure radial velocities and to determine chemical abundances using the MyGIsFOS code. Results.We developed a likelihood model that takes metallicity and radial velocities into account. We conclude that 12 stars are likely members of C-19, while 3 stars (S05, S12, and S13) are likely contaminants. When these 3 stars are excluded, our model implies a mean metallicity 〈[Fe/H]〉 = −3.1 ± 0.1, the mean radial velocity is 〈v_r〉 = −192 ± 3km s⁻¹, and the velocity dispersion is σ_vr= 5.9_−5.9^+3.6km s⁻¹. This all agrees within errors with previous studies. The A(Mg) of a sample of 15 C-19 members, including 6 giant stars, shows a standard deviation of 0.44 dex, and the mean uncertainty on Mg is 0.25 dex. Conclusions.Our preferred interpretation of the current data is that C-19 is a disrupted GC. We cannot completely rule out the possibility that the GC could have belonged to a dwarf galaxy that contained more metal-rich stars, however. This scenario would explain the radial velocity members at higher metallicity, as well as the wth and velocity dispersion of the stream. In either case, a GC formed out of gas as poor in metals as these stars seems necessary to explain the existence of C-19. The possibility that no GC was associated with C-19 cannot be ruled out either. 

Plants respond to rapid environmental change in ways that depend on both their genetic identity and their phenotypic plasticity, impacting their survival as well as associated ecosystems. However, genetic and environmental effects on phenotype are difficult to quantify across large spatial scales and through time. Leaf hyperspectral reflectance offers a potentially robust approach to map these effects from local to landscape levels. Using a handheld field spectrometer, we analyzed leaf‐level hyperspectral reflectance of the foundation tree species Populus fremontii in wild populations and in three 6‐year‐old experimental common gardens spanning a steep climatic gradient. First, we show that genetic variation among populations and among clonal genotypes is detectable with leaf spectra, using both multivariate and univariate approaches. Spectra predicted population identity with 100% accuracy among trees in the wild, 87%–98% accuracy within a common garden, and 86% accuracy across different environments. Multiple spectral indices of plant health had significant heritability, with genotype accounting for 10%–23% of spectral variation within populations and 14%–48% of the variation across all populations. Second, we found gene by environment interactions leading to population‐specific shifts in the spectral phenotype across common garden environments. Spectral indices indicate that genetically divergent populations made unique adjustments to their chlorophyll and water content in response to the same environmental stresses, so that detecting genetic identity is critical to predicting tree response to change. Third, spectral indicators of greenness and photosynthetic efficiency decreased when populations were transferred to growing environments with higher mean annual maximum temperatures relative to home conditions. This result suggests altered physiological strategies further from the conditions to which plants are locally adapted. Transfers to cooler environments had fewer negative effects, demonstrating that plant spectra show directionality in plant performance adjustments. Thus, leaf reflectance data can detect both local adaptation and plastic shifts in plant physiology, informing strategic restoration and conservation decisions by enabling high resolution tracking of genetic and phenotypic changes in response to climate change. 

Abstract Supernova (SN) 2014C is a rare transitional event that exploded as a hydrogen-poor, helium-rich Type Ib SN and subsequently interacted with a hydrogen-rich circumstellar medium (CSM) a few months postexplosion. This unique interacting object provides an opportunity to probe the mass-loss history of a stripped-envelope SN progenitor. Using the James Webb Space Telescope (JWST), we observed SN 2014C with the Mid-Infrared Instrument Medium Resolution Spectrometer at 3477 days postexplosion (rest frame), and the Near-Infrared Spectrograph Integral Field Unit at 3568 days postexplosion, covering 1.7–25μm. The bolometric luminosity indicates that the SN is still interacting with the same CSM that was observed with the Spitzer Space Telescope 40–1920 days postexplosion. JWST spectra and near-contemporaneous optical and near-infrared spectra show strong [Neii] 12.831μm, He 1.083μm, Hα, and forbidden oxygen ([Oi]λλ6300, 6364, [Oii]λλ7319, 7330, and [Oiii]λλ4959, 5007) emission lines with asymmetric profiles, suggesting a highly asymmetric CSM. The mid-IR continuum can be explained by ∼0.036M_⊙of carbonaceous dust at ∼300 K and ∼0.043M_⊙of silicate dust at ∼200 K. The observed dust mass has increased tenfold since the last Spitzer observation 4 yr ago, with evidence suggesting that new grains have condensed in the cold dense shell between the forward and reverse shocks. This dust mass places SN 2014C among the dustiest SNe in the mid-IR and supports the emerging observational trend that SN explosions produce enough dust to explain the observed dust mass at high redshifts.