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A powerful technique to trace the signatures of the first stars is through the metal enrichment in concentrated reservoirs of hydrogen, such as the damped Lyα absorbers (DLAs) in the early Universe. We conducted a survey aimed at discovering DLAs along sight lines to high-z quasars in order to measure element abundances at z > 4. Here we report our first results from this survey for 10 DLAs with redshifts of ≈4.2–5.0. We determine abundances of C, O, Si, S, and Fe, and thereby the metallicities and dust depletions. We find that DLA metallicities at z > 4.5 show a wide diversity spanning ∼3 orders of magnitude. The metallicities of DLAs at 3.7 < z < 5.3 show a larger dispersion compared to that at lower redshifts. Combining our sample with the literature, we find a relatively smooth evolution of metallicity with redshift out to z ∼ 5.3, with a tentative (∼2 sigma) indication of a slight rise in metallicity at 4.5 < z < 5.3. The relative abundances exhibit C enhancement for both metal-poor and metal-enriched DLAs. In addition, α-element enhancement is evident in some DLAs, including a DLA at z = 4.7 with a supersolar metallicity. Comparing [C/O] and [Si/O] with model predictions, four DLAs in our survey seem consistent with a nonzero Population III contribution (three with >~30% Population III contribution). Combining our sample and the literature, we find the dust depletion strength and dust-to-metal ratios to correlate positively with the total (gas+solid phase) metallicity, confirming the presence of metal-rich, dusty DLAs even at ∼1 billion years after the Big Bang. 

We present a study of new 7.7–11.3 μm data obtained with theJames WebbSpace Telescope Mid-InfraRed Instrument in the starburst galaxy M 82. In particular, we focus on the dependency of the integrated CO(1–0) line intensity on the MIRI-F770W and MIRI-F1130W filter intensities to investigate the correlation between H₂content and the 7.7 and 11.3 μm features from polycyclic aromatic hydrocarbons (PAH) in M 82’s outflows. To perform our analysis, we identify CO clouds using the archival¹²CO(J = 1 − 0) NOEMA moment 0 map within 2 kpc from the center of M 82, with sizes ranging between ∼21 and 270 pc; then, we compute the CO-to-PAH relations for the 306 validated CO clouds. On average, the power-law slopes for the two relations in M 82 are lower than what is seen in local main-sequence spirals. In addition, there is a moderate correlation betweenI_{CO(1 − 0)} − I_7.7 μm/I_11.3 μmfor some of the CO cloud groups analyzed in this work. Our results suggest that the extreme conditions in M 82 translate into CO not tracing the full budget of molecular gas in smaller clouds, perhaps as a consequence of photoionization and/or emission suppression of CO molecules due to hard radiation fields from the central starburst. 

Abundances of chemical elements in the interstellar and circumgalactic media of high-redshift galaxies offer important constraints on the nucleosynthesis by early generations of stars. Damped Lyα absorbers (DLAs) in spectra of high-redshift background quasars are excellent sites for obtaining robust measurements of element abundances in distant galaxies. Past studies of DLAs at redshifts z > 4 have measured abundances of 0.01 solar. Here we report the discovery of a DLA at z = 4.7372 with an exceptionally high degree of chemical enrichment. We estimate the H I column density in this absorber to be log (NH I/cm^−2) = 20.48 ± 0.15. Our analysis shows unusually high abundances of carbon and oxygen ([C/H] = 0.88 ± 0.17, [O/H] = 0.71 ± 0.16). Such a high level of enrichment a mere 1.2 Gyr after the Big Bang is surprising because of insufficient time for the required amount of star formation. To our knowledge, this is the first supersolar absorber found at z > 4.5. We find the abundances of Si and Mg to be [Si/H] = -0.56-0.35+0.40 and [Mg/H] = -0.59-0.50+0.27, confirming the metal-rich nature of this absorber. By contrast, Fe shows a much lower abundance ([Fe/H] = -1.53 ± 0.15). We discuss implications of our results for galactic chemical evolution models. The metallicity of this absorber is higher than that of any other known DLA and is >2 orders of magnitude above predictions of chemical evolution models and the NH I-weighted mean metallicity from previous studies at z > 4.5. The relative abundances (e.g., [O/Fe] = 2.29 ± 0.05, [C/Fe] = 2.46 ± 0.08) are also highly unusual compared to predictions for enrichment by early stars. 

Photoswitches are molecules that undergo a reversible, structural isomerization after exposure to different wavelengths of light. The dynamic control offered by molecular photoswitches is favorable for applications in materials chemistry, photopharmacology, and catalysis. Ideal photoswitches absorb visible light and have long-lived metastable isomers. We used high throughput virtual screening to predict the absorption maxima (λmax) of the E-isomer and half-lives (t1/2) of the Z-isomer. However, computing the photophysical and kinetic properties of each entry of a virtual molecular library containing 103–106 entries with density functional theory is prohibitively time-consuming. We applied active search, a machine learning technique to intelligently search a chemical search space of 255991 photoswitches based on 29 known azoarenes and their derivatives. We iteratively trained the active search algorithm based on whether a candidate absorbed visible light (λmax > 450 nm). Active search was found to triple the discovery rate compared to random search. Further, we projected 1962 photoswitches to 2D using the Uniform Manifold Approximation and Projection (umap) algorithm and found that λmax depends on the core, which is tunable with substituents. We then incorporated a second stage of screening with to predict the stabilities of the Z-isomers for the top 1% of candidates. We identified four ideal photoswitches that concurrently satisfy λmax > 450 nm and t1/2 > 2 hours; the range of λmax and t1/2 range from 465 to 531 nm and hours to years, respectively. 

ABSTRACT We investigate the abundance and distribution of metals in the high-redshift intergalactic medium and circum-galactic medium through the analysis of a sample of almost 600 Si iv absorption lines detected in high- and intermediate-resolution spectra of 147 quasars. The evolution of the number density of Si iv lines, the column density distribution function, and the cosmic mass density are studied in the redshift interval 1.7 ≲ z ≲ 6.2 and for log N(Si iv) ≥ 12.5. All quantities show a rapid increase between z ∼ 6 and z ≲ 5 and then an almost constant behaviour to z ∼ 2 in very good agreement with what is already observed for C iv absorption lines. The present results are challenging for numerical simulations: When simulations reproduce our Si iv results, they tend to underpredict the properties of C iv, and when the properties of C iv are reproduced, the number of strong Si iv lines [log N(Si iv) > 14] is overpredicted.