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We report unambiguous spectroscopic evidence of peptide bond formation at the air–water interface, yielding a possible mechanism providing insight into the formation of modern ribosomal peptide bonds, and a means for the emergence of peptides on early Earth. Protein synthesis in aqueous environments, facilitated by sequential amino acid condensation forming peptides, is a ubiquitous process in modern biology, and a fundamental reaction necessary in prebiotic chemistry. Such reactions, however, are condensation reactions, requiring the elimination of a water molecule for every peptide bond formed, and are thus unfavorable in aqueous environments both from a thermodynamic and kinetic point of view. We use the hydrophobic environment of the air–water interface as a favorable venue for peptide bond synthesis, and demonstrate the occurrence of this chemistry with in situ techniques using Langmuir-trough methods and infrared reflection absorption spectroscopy. Leucine ethyl ester (a small amino acid ester) first partitions to the water surface, then coordinates with Cu ²⁺ ions at the interface, and subsequently undergoes a condensation reaction selectively forming peptide bonds at the air–water interface.

Marine barite (BaSO4) is a relatively ubiquitous, though minor, component of ocean sediments. Modern studies of the accumulation of barite in ocean sediments have demonstrated a robust correlation between barite accumulation rates and carbon export to the deep ocean. This correlation has been used to develop quantitative relationships between barite accumulation rates and export production and is used to reconstruct export production in the geologic past, particularly during times of dynamic changes in the carbon cycle. We review the processes that affect the formation and preservation of marine barite, as well as those controlling the relationship between the barium (Ba) and carbon biogeochemical cycles. Additionally, we take a new approach to modeling the marine Ba cycle as a two-box model, specifically evaluating Ba utilization in the surface ocean and refining the equation describing the relationship between export production and barite formation. We compare these new results with past modeling efforts. The new model demonstrates that increases in export production can lead to sustained increases in barite accumulation in marine sediments without resulting in complete surface water Ba depletion, which is distinctly different from previous modeling results.

The study of organic chemistry in atmospheric aerosols and cloud formation is of interest in predictions of air quality and climate change. It is now known that aqueous phase chemistry is important in the formation of secondary organic aerosols. Here, the photoreactivity of pyruvic acid (PA; CH ₃COCOOH) is investigated in aqueous environments characteristic of atmospheric aerosols. PA is currently used as a proxy for α-dicarbonyls in atmospheric models and is abundant in both the gas phase and the aqueous phase (atmospheric aerosols, fog, and clouds) in the atmosphere. The photoreactivity of PA in these phases, however, is very different, thus prompting the need for a mechanistic understanding of its reactivity in different environments. Although the decarboxylation of aqueous phase PA through UV excitation has been studied for many years, its mechanism and products remain controversial. In this work, photolysis of aqueous PA is shown to produce acetoin (CH ₃CHOHCOCH ₃), lactic acid (CH ₃CHOHCOOH), acetic acid (CH ₃COOH), and oligomers, illustrating the progression from a three-carbon molecule to four-carbon and even six-carbon molecules through direct photolysis. These products are detected using vibrational and electronic spectroscopy, NMR, and MS, and a reaction mechanism is presented accounting for all products detected. The relevance of sunlight-initiated PA chemistry in aqueous environments is then discussed in the context of processes occurring on atmospheric aerosols.

Variations in speleothem calcium isotope ratios (δ44Ca) are thought to be uniquely controlled by prior carbonate precipitation (PCP) above a drip site and, when calibrated with modern data, show promise as a semi‐quantitative proxy for paleorainfall. However, few monitoring studies have focused on δ44Ca in modern cave systems. We present a multi‐year comparative study of δ44Ca, carbon isotopes (δ13C), and trace elemental ratios from cave drip waters, modern calcite, and host rocks from two cave systems in California—White Moon Cave (WMC) and Lake Shasta Caverns (LSC). Drip water and calcite δ44Ca from both caves indicate PCP‐driven enrichment, and we used a simple Rayleigh fractionation model to quantify PCP variability over the monitoring period. Modern calcite trace element and δ44Ca data positively correlate at WMC, but not at LSC, indicating a shared PCP control on these proxies at WMC but not at LSC. At both WMC and LSC, we observe an inverse relationship between PCP and rainfall amounts, though this relationship is variable across individual drip sites. Our modeled data suggest that WMC experiences ∼20% more PCP than LSC, consistent with the fact that WMC receives less annual rainfall. This work supports speleothem δ44Ca as an independent constraint on PCP that can aid in the interpretation of other hydrologically sensitive proxies and provide quantitative estimates of paleorainfall. Additional, long‐term monitoring studies from a variety of climate settings will be key for understanding δ44Ca variability in cave systems more fully and better constraining the relationship between PCP and rainfall. Plain Language Summary Chemical analyses on the minerals that make up stalagmites can provide useful information about how rainfall varied in the past, but most of the chemical parameters measured in stalagmites can respond to several complex environmental influences in addition to rainfall amount. Stalagmite calcium (Ca) isotope ratios can provide more direct information about past rainfall variability but haven't been closely studied in modern cave systems. In this study, we present new Ca isotope measurements of cave drip waters and modern calcite mineral samples collected at a seasonal‐to‐annual resolution from two sites in California that experience different amounts of yearly rainfall. We find that periods of less rainfall at each individual cave generally correspond to higher Ca isotope ratios and that the drier of the two caves experienced less water infiltration overall during the study period. These findings support the idea that Ca isotope ratios in cave systems are controlled by the amount of water infiltrating the cave and can be used in combination with other data from stalagmites to reconstruct rainfall variability in the past. This type of information about past rainfall patterns can help planners assess future water availability, which is especially important in drought‐prone regions such as California. Key Points Drier periods correspond to higher Ca isotope ratios and more prior calcite precipitation, though there is variability between drip sites Modern calcite trace element ratios positively correlate with Ca isotope data at one of the two cave sites Ca isotope data provides an independent constraint on water infiltration to aid the interpretation of other hydrologically sensitive proxies

A common approach to attract students in the United States to the geosciences is to emphasize outdoor experiences in the natural world. However, it is unclear how successful this strategy is. Specifically, the geosciences have been less successful than other sciences at recruiting a diverse workforce that reflects different perspectives and life experiences. Here we present a survey of students enrolled in College Algebra at a Hispanic-serving institution in the southwestern United States where, of 1550 students surveyed, 55.3% identified as an underrepresented minority (URM). We find that surveyed students care little about working outdoors. Instead, they rate altruistic factors, such as helping people or the environment, as most important. Female respondents rate these factors higher than male respondents. We also find that many respondents know little about what a career in geoscience entails. We argue that better informing students about the altruistic potential of geoscience careers would be an effective strategy to broaden recruitment.

Testis-restricted melanoma antigen (MAGE) proteins are frequently hijacked in cancer and play a critical role in tumorigenesis. MAGEs assemble with E3 ubiquitin ligases and function as substrate adaptors that direct the ubiquitination of novel targets, including key tumor suppressors. However, how MAGEs recognize their targets is unknown and has impeded the development of MAGE-directed therapeutics. Here, we report the structural basis for substrate recognition by MAGE ubiquitin ligases. Biochemical analysis of the degron motif recognized by MAGE-A11 and the crystal structure of MAGE-A11 bound to the PCF11 substrate uncovered a conserved substrate binding cleft (SBC) in MAGEs. Mutation of the SBC disrupted substrate recognition by MAGEs and blocked MAGE-A11 oncogenic activity. A chemical screen for inhibitors of MAGE-A11:substrate interaction identified 4-Aminoquinolines as potent inhibitors of MAGE-A11 that show selective cytotoxicity. These findings provide important insights into the large family of MAGE ubiquitin ligases and identify approaches for developing cancer-specific therapeutics. Testis-restricted melanoma antigen (MAGE) proteins function as substrate adapters for E3 ubiquitin ligases. Biochemical and structural analyses of MAGE-A11 provide insight into the substrate binding mode of MAGE proteins and enable discovery of potent, cytotoxic inhibitors of MAGE-A11:substrate interaction.

Background This implementation feasibility study was conducted to determine whether an evidence-based parent-implemented distance-learning intervention model for young children at high likelihood of having ASD could be implemented at fidelity by Part C community providers and by parents in low-resource communities. Methods The study used a community-academic partnership model to adapt an evidence-based intervention tested in the current pilot trial involving randomization by agency in four states and enrollment of 35 coaches and 34 parent-family dyads. After baseline data were gathered, providers in the experimental group received 12–15 h of training while control providers received six webinars on early development. Providers delivered 6 months of intervention with children-families, concluding with data collection. Regression analyses were used to model outcomes of the coach behaviors, the parent fidelity ratings, and child outcomes. Results A block design model-building approach was used to test the null model followed by the inclusion of group as a predictor, and finally the inclusion of the planned covariates. Model fit was examined using changes in R 2 and F -statistic. As hypothesized, results demonstrated significant gains in (1) experimental provider fidelity of coaching implementation compared to the control group; and (2) experimental parent fidelity of implementation compared to the control group. There were no significant differences between groups on child developmental scores. Conclusions Even though the experimental parent group averaged less than 30 min of intervention weekly with providers in the 6 months, both providers and parents demonstrated statistically significant gains on the fidelity of implementation scores with moderate effect sizes compared to control groups. Since child changes in parent-mediated models are dependent upon the parents’ ability to deliver the intervention, and since parent delivery is dependent upon providers who are coaching the parents, these results demonstrated that two of these three links of the chain were positively affected by the experimental implementation model. However, a lack of significant differences in child group gains suggests that further work is needed on this model. Factors to consider include the amount of contact with the provider, the amount of practice children experience, the amount of contact both providers and parents spend on training materials, and motivational strategies for parents, among others. Trial registration Registry of Efficacy and Effectiveness Studies: #4360, registered 1xx, October, 2020 – Retrospectively registered, https://sreereg.icpsr.umich.edu/sreereg/