Phosphorylation in liquid sulfur dioxide under prebiotically plausible conditions

In nature, organophosphates provide key functions such as information storage and transport, structural tasks, and energy transfer. Since condensations are unfavourable in water and nucleophilic attack at phosphate is kinetically inhibited, various abiogenesis hypotheses for the formation of organophosphate are discussed. Recently, the application of phosphites as phosphorylation agent showed promising results. However, elevated temperatures and additional reaction steps are required to obtain organophosphates. Here we show that in liquid sulfur dioxide, which acts as solvent and oxidant, efficient organophosphate formation is enabled. Phosphorous acid yields up to 32.6% 5′ nucleoside monophosphate, 3.6% 5′ nucleoside diphosphate, and the formation of nucleoside triphosphates and dinucleotides in a single reaction step at room temperature. In addition to the phosphorylation of organic compounds, we observed diserine formation. Thus, we suggest volcanic environments as reaction sites for biopolymer formation on Early Earth. Because of the simple recyclability of sulfur dioxide, the reaction is also interesting for synthesis chemistry

Iron-Mediated Peptide Formation in Water and Liquid Sulfur Dioxide under Prebiotically Plausible Conditions

Peptides have essential structural and catalytic functions in living organisms. The formation of peptides requires the overcoming of thermodynamic and kinetic barriers. In recent years, various formation scenarios that may have occurred during the origin of life have been investigated, including iron(III)-catalyzed condensations. However, iron(III)-catalysts require elevated temperatures and the catalytic activity in peptide bond forming reactions is often low. It is likely that in an anoxic environment such as that of the early Earth, reduced iron compounds were abundant, both on the Earth's surface itself and as a major component of iron meteorites. In this work, we show that reduced iron activated by acetic acid mediates efficiently peptide formation. We recently demonstrated that, compared to water, liquid sulfur dioxide (SO2) is a superior reaction medium for peptide formations. We thus investigated both and observed up to four amino acid/peptide coupling steps in each solvent. Reaction with diglycine (G(2)) formed 2.0 % triglycine (G(3)) and 7.6 % tetraglycine (G(4)) in 21 d. Addition of G(3) and dialanine (A(2)) yielded 8.7 % G(4). Therefore, this is an efficient and plausible route for the formation of the first peptides as simple catalysts for further transformations in such environments

Optimizing Sponsored Humanitarian Parole

The United States has introduced a special humanitarian parole process for Ukrainian citizens in response to Russia 2022 invasion of Ukraine. To qualify for parole, Ukrainian applicants must have a sponsor in the United States. In collaboration with HIAS, a refugee resettlement agency involved in the parole process, we deployed RUTH (Refugees Uniting Through HIAS), a novel algorithmic matching system that is driven by the relocation preferences of refugees and the priorities of US sponsors. RUTH adapts Thakral Multiple-Waitlist Procedure (MWP) that combines the main FIFO queue with location-specific FIFO queues to effectively manage the preferences of refugees and the supply of community sponsors. RUTH also incorporates various feasibility considerations, such as community capacity religious, and medical needs. The adapted mechanism is envy-free, efficient, and strategy-proof for refugees. Our analysis shows diverse refugee location preferences, not fully explained by observables, highlighting the challenge of predicting preferences directly from them. We use our data for two counterfactual simulations. First, we consider the effects of increased waiting times for refugees on the quality of their matches. We find that with a periodic Top Trading Cycles algorithm, increasing period length from 24 days to 80 days improves the average rank of a refugees match from 3.20 to 2.44. Second, we estimate the arrival rates of sponsors in each location that would be consistent with a long-run steady state. We find that more desirable locations (regarding refugee preferences) require the highest arrival rates, suggesting that preferences might be a useful indicator for investments in sponsorship capacity. Our study highlights the potential for preference-based algorithms such as RUTH to improve the efficiency and fairness of other rapidly deployed humanitarian parole processes.Comment: In Equity and Access in Algorithms, Mechanisms, and Optimization (EAAMO23), October 30-November 1, 2023, Boston, MA, USA. 34 pages, including an appendi

Data-Based Supply Chain Collaboration - Improving Product Quality in Global Production Networks by Sharing Information

In times of globalization and digitalization, silo mentality and protectionism lead to competitive disadvantages for all partners of a production network. High scrap rates and low supplier margins in the production of high-precision products can be identified as resulting inefficiencies. Supply chain collaboration can contribute to significantly increase product quality by simultaneously reducing the associated costs, globally. We introduce batch allocation as a data-driven method for cross-company quality control of differing component batches based on both, supplier data and internal data. The industrial application is demonstrated within a global production network for manufacturing high-precision products

Scenario Human Centered Manufacturing (Man-u-Faktur 2012)

Unter Ambient Intelligence (AmI) wird die Integration verschiedener Technologien zu einer den Menschen umgebenden, (nahezu) unsichtbaren Gesamtheit verstanden. Diese Intelligente Umgebung wird möglich durch die Miniaturisierung hochintegrierter Bauteile (Sensoren, Aktuatoren und Rechnern), deren zunehmende Intelligenz und vor allem deren lokale und globale zunehmend drahtlose Vernetzung. Unter dem Titel Man-u-Faktur 2012 (man and factoring in 2012) wurde an der Technischen Universität Kaiserslautern im Rahmen des Forschungsschwerpunkts Ambient Intelligence ein Szenario entwickelt, das ein beeindruckendes Gesamtbild einer Technik, die den Menschen in den Mittelpunkt rückt, beschreibt. Man-u-Faktur 2012 steht dabei für ein Weiterdrehen des Rads der Industrialisierung von der heute üblichen variantenreichen, technologiezentrierten Massenfertigung hin zu einer kundenindividuellen, mitarbeiterzentrierten Maßfertigung. Im Speziellen wird hierunter der Aufbau massiv verteiler kunden- aber auch mitarbeiterfreundlicher Produktionsanlagen verstanden, die sich im hochdynamischen Umfeld entsprechend der jeweiligen Gegebenheiten anzupassen wissen. Der Mensch ist überall dort präsent, wo flexibles Arbeiten oder flexible Entscheidungen im Vordergrund stehen. In diesem Bericht wird der Einfluss von Ambient Intelligence beispielhaft auf die Vision einer Fahrradproduktion in der Man-u-Faktur 2012 angewandt. Aus diesem Szenario werden anschließend sowohl die zu entwickelnden Schlüsseltechnologien als auch die Einflüsse auf Wirtschaft und Gesellschaft abgeleitet.Ambient Intelligence (AmI) is the vision of a Society where the emphasis is on greater user-friendliness, more efficient services support, user-empowerment, and support for human interactions. People are surrounded by intelligent intuitive interfaces that are embedded in all kinds of objects and an environment that is capable of recognising and responding to the presence of different individuals in a seamless, unobtrusive and often invisible way. An interdisciplinary team from The University of Kaiserslautern (research cluster Ambient Intelligence) developed the scenario Man-u-Faktur 2012, which draws up an awe-inspiring picture of future technology having integrated man into complex production chains. Man-u-Faktur 2012 (man and factoring in 2012) is the idea of bringing man back into the factories by still walking on the trail of industrialization, heading towards a customer oriented production. In fact, that will be the begin of massively distributed customer and worker friendly plants, which will be able to adapt to (nearly) every situation within a highly dynamical process. There will be a huge product range produced in one factory. Respect towards energy and other environmental problems will play an important role. Yet, man should be the center of all actions. He will be present in particular where we need flexible decisions as well as flexible work. In this report the influence of Ambient Intelligence is focused on the vision of a bicycle production in the Man-u-Faktur 2012. From this scenario the necessary key technologies as well as the impacts on society and economy are derived

In Situ Mass Spectrometric and Kinetic Investigations of Soai's Asymmetric Autocatalysis

Chemical reactions that lead to a spontaneous symmetry breaking or amplification of the enantiomeric excess are of fundamental interest in explaining the formation of a homochiral world. An outstanding example is Soai's asymmetric autocatalysis, in which small enantiomeric excesses of the added product alcohol are amplified in the reaction of diisopropylzinc and pyrimidine‐5‐carbaldehydes. The exact mechanism is still in dispute due to complex reaction equilibria and elusive intermediates. In situ high‐resolution mass spectrometric measurements, detailed kinetic analyses and doping with in situ reacting reaction mixtures show the transient formation of hemiacetal complexes, which can establish an autocatalytic cycle. We propose a mechanism that explains the autocatalytic amplification involving these hemiacetal complexes. Comprehensive kinetic experiments and modelling of the hemiacetal formation and the Soai reaction allow the precise prediction of the reaction progress, the enantiomeric excess as well as the enantiomeric excess dependent time shift in the induction period. Experimental structural data give insights into the privileged properties of the pyrimidyl units and the formation of diastereomeric structures leading to an efficient amplification of even minimal enantiomeric excesses, respectively

From amino acid mixtures to peptides in liquid sulphur dioxide on early Earth

The formation of peptide bonds is one of the most important biochemical reaction steps. Without the development of structurally and catalytically active polymers, there would be no life on our planet. However, the formation of large, complex oligomer systems is prevented by the high thermodynamic barrier of peptide condensation in aqueous solution. Liquid sulphur dioxide proves to be a superior alternative for copper-catalyzed peptide condensations. Compared to water, amino acids are activated in sulphur dioxide, leading to the incorporation of all 20 proteinogenic amino acids into proteins. Strikingly, even extremely low initial reactant concentrations of only 50 mM are sufficient for extensive peptide formation, yielding up to 2.9% of dialanine in 7 days. The reactions carried out at room temperature and the successful use of the Hadean mineral covellite (CuS) as a catalyst, suggest a volcanic environment for the formation of the peptide world on early Earth

Chiral stationary phases and applications in gas chromatography

Chiral compounds are ubiquitous in nature and play a pivotal role in biochemical processes, in chiroptical materials and applications, and as chiral drugs. The analysis and determination of the enantiomeric ratio (er) of chiral compounds is of enormous scientific, industrial, and economic importance. Chiral separation techniques and methods have become indispensable tools to separate chiral compounds into their enantiomers on an analytical as well on a preparative level to obtain enantiopure compounds. Chiral gas chromatography and high-performance liquid chromatography have paved the way and fostered several research areas, that is, asymmetric synthesis and catalysis in organic, medicinal, pharmaceutical, and supramolecular chemistry. The development of highly enantioselective chiral stationary phases was essential. In particular, the elucidation and understanding of the underlying enantioselective supramolecular separation mechanisms led to the design of new chiral stationary phases. This review article focuses on the development of chiral stationary phases for gas chromatography. The fundamental mechanisms of the recognition and separation of enantiomers and the selectors and chiral stationary phases used in chiral gas chromatography are presented. An overview over syntheses and applications of these chiral stationary phases is presented as a practical guidance for enantioselective separation of chiral compound classes and substances by gas chromatography

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