Contribution of Enzyme Catalysis to the Achievement of the United Nations’ Sustainable Development Goals

In September 2015, the United Nations General Assembly established the 2030 Agenda for Sustainable Development, which includes 17 Sustainable Development Goals (SDGs). The interlinked SDGs are intended to be a ‘shared blueprint for peace and prosperity for people and the planet, now and in the future’ (https://sdgs.un.org/SDGs, accessed on 28 April 2023). The agenda emphasizes a holistic approach to achieving sustainable development for all, balancing the economic, social, and environmental dimensions of sustainable development. The agenda recognizes that ending poverty and other forms of deprivation must align with strategies that improve health and education, reduce inequality, and promote economic growth—all while tackling climate change and working to preserve our oceans and forests. Implementing the SDGs will require collaboration between different actors in government, industry, and civil society, as well as scientists from different disciplines. In the scientific community, the SDGs should provide a framework and serve as the guiding principles for research activity. Enzyme catalysis, among many other disciplines, can could represent a valuable contribution to the SDGs. The aim of this editorial chapter is to highlight the potential of enzyme catalysis in achieving the SDGs and to contribute to the realization of a ‘better world’, while reflecting on the deployment of these technologies to achieve these goals

PFNs Are Flexible Models for Real-World Bayesian Optimization

In this paper, we use Prior-data Fitted Networks (PFNs) as a flexible surrogate for Bayesian Optimization (BO). PFNs are neural processes that are trained to approximate the posterior predictive distribution (PPD) for any prior distribution that can be efficiently sampled from. We describe how this flexibility can be exploited for surrogate modeling in BO. We use PFNs to mimic a naive Gaussian process (GP), an advanced GP, and a Bayesian Neural Network (BNN). In addition, we show how to incorporate further information into the prior, such as allowing hints about the position of optima (user priors), ignoring irrelevant dimensions, and performing non-myopic BO by learning the acquisition function. The flexibility underlying these extensions opens up vast possibilities for using PFNs for BO. We demonstrate the usefulness of PFNs for BO in a large-scale evaluation on artificial GP samples and three different hyperparameter optimization testbeds: HPO-B, Bayesmark, and PD1. We publish code alongside trained models at http://github.com/automl/PFNs4BO.Comment: Accepted at ICML 202

P450BM3-Catalyzed Oxidations Employing Dual Functional Small Molecules

A set of dual functional small molecules (DFSMs) containing different amino acids has been synthesized and employed together with three different variants of the cytochrome P450 monooxygenase P450BM3 from Bacillus megaterium in H2O2-dependent oxidation reactions. These DFSMs enhance P450BM3 activity with hydrogen peroxide as an oxidant, converting these enzymes into formal peroxygenases. This system has been employed for the catalytic epoxidation of styrene and in the sulfoxidation of thioanisole. Various P450BM3 variants have been evaluated in terms of activity and selectivity of the peroxygenase reactions.MINECO-CTQ2016-76908-C2-1,2-PComisión Europea de Investigación-ERC-648026Unión Europea-H2020-BBI-PPP-2015-2-1-720297Organización Holandesa de Investigación Científica (VICI)-724.014.00

Expression and characterization of the nitrile reductase queF from E. coli

AbstractThe expression and characterization of a nitrile reductase from Escherichia coli K-12 (EcoNR), a newly discovered enzyme class, is described. This enzyme has a potential application for an alternative nitrile reduction pathway. The enzyme activity towards its natural substrate, preQ0, was demonstrated and optimal working conditions were found to be at 37°C and at pH 7 with Tris buffer

Enzymatic Bromocyclization of alpha- and gamma-Allenols by Chloroperoxidase from Curvularia inaequalis

Vanadate-dependent chloroperoxidase from Curvularia inaequalis catalyzes 5-endo-trig bromocyclizations of alpha-allenols to produce valuable halofunctionalized furans as versatile synthetic building blocks. In contrast to other haloperoxidases, also the more challenging 5-exo-trig halocyclizations of gamma-allenols succeed with this system even though the scope still remains more narrow. Benefitting from the vanadate chloroperoxidase's high resiliency towards oxidative conditions, cyclization-inducing reactive hypohalite species are generated in situ from bromide salts and hydrogen peroxide. Crucial requirements for high conversions are aqueous biphasic emulsions as reaction media, stabilized by either cationic or non-ionic surfactants.Peer reviewe

H2 as a fuel for flavin- and H2O2-dependent biocatalytic reactions

The soluble hydrogenase from Ralstonia eutropha provides an atom efficient regeneration system for reduced flavin cofactors using H2 as an electron source. We demonstrated this system for highly selective ene-reductase-catalyzed C[double bond, length as m-dash]C-double bond reductions and monooxygenase-catalyzed epoxidation. Reactions were expanded to aerobic conditions to supply H2O2 for peroxygenase-catalyzed hydroxylations.DFG, 284111627, H2-basierende Kaskaden für die Biosynthese von N-HeterocyclenDFG, 405325648, ,Engineering von O2-toleranten Hydrogenasen und ihre physiologischen Auswirkungen in rekombinanten Bakterien im Hinblick auf die Hydrogenase-abhängige NAD(P)H-Regeneration und H2-ProduktionDFG, 390540038, EXC 2008: UniSysCatTU Berlin, Open-Access-Mittel - 202

Knowledge is power: A theory of information, income and welfare spending

No voters cast their votes based on perfect information, but better educated and richer voters are on average better informed than others. We develop a model where the voting mistakes resulting from low political knowledge reduce the weight of poor voters, and cause parties to choose political platforms that are better aligned with the preferences of rich voters. In US election survey data, we find that income is more important in affecting voting behavior for more informed voters than for less informed voters, as predicted by the model. Further, in a panel of US states we find that when there is a strong correlation between income and political information, Congress representatives vote more conservatively, which is also in line with our theory.Political Economics

Asymmetric azidohydroxylation of styrene derivatives mediated by a biomimetic styrene monooxygenase enzymatic cascade

Enantioenriched azido alcohols are precursors for valuable chiral aziridines and 1,2-amino alcohols, however their chiral substituted analogues are difficult to access. We established a cascade for the asymmetric azidohydroxylation of styrene derivatives leading to chiral substituted 1,2-azido alcohols via enzymatic asymmetric epoxidation, followed by regioselective azidolysis, affording the azido alcohols with up to two contiguous stereogenic centers. A newly isolated two-component flavoprotein styrene monooxygenase StyA proved to be highly selective for epoxidation with a nicotinamide coenzyme biomimetic as a practical reductant. Coupled with azide as a nucleophile for regioselective ring opening, this chemo-enzymatic cascade produced highly enantioenriched aromatic α-azido alcohols with up to >99% conversion. A bi-enzymatic counterpart with halohydrin dehalogenase-catalyzed azidolysis afforded the alternative β-azido alcohol isomers with up to 94% diastereomeric excess. We anticipate our biocatalytic cascade to be a starting point for more practical production of these chiral compounds with two-component flavoprotein monooxygenases. A one-pot enzymatic cascade for the asymmetric azidohydroxylation of styrenes leads to chiral 1,2-azido alcohols with up to two stereocenters

Energising the E-factor: The E+-factor

[EN] The E-factor has become an important measure for the environmental impact of (bio)chemical reactions. However, summing up the obvious wastes generated in the laboratory neglects energy-related wastes (mostly greenhouse gases) which are generated elsewhere. To estimate these wastes, we propose to extend the E-factor by an energy-term (E-factor). At the example of a lab-scale enzyme fermentation, we demonstrate that the E-factor can constitute a multiple of the classical E-factor and therefore must not be neglected striving for a holistic estimation of the environmental impact.This workwas supported by the European Union Project H2020-BBI-PPP-2015-2-720297-ENZOX2 and F.H. gratefully acknowledges funding by European Research Council (ERC Consolidator Grant No. 648026) and the for financial support through a Netherlands Organisation for Scientific Research VICI grant (no. 724.014.003). J.M.R, B.R and A.S.B. gratefully acknowledge support from the United States National Science Foundation grant IIP-1540017

Coagulation using organic carbonates opens up a sustainable route towards regenerated cellulose films

Due to their biodegradability, biocompatibility and sustainable nature, regenerated cellulose (RC) films are of enormous relevance for green applications including medicinal, environmental and separation technologies. However, the processes used so far are very hazardous to the environment and health. Here, we disclose a simple, fast, environmentally friendly, nontoxic and cost-effective processing method for preparing RC films. High quality non-transparent and transparent RC films and powders can be produced by dissolution with tetrabutylphosphonium hydroxide [TBPH]/[TBP]+[OH]− followed by coagulation with organic carbonates. Investigations on the coagulation mechanism revealed an extremely fast reaction between the carbonates and the hydroxide ions. The high-quality powders and films were fully characterized with respect to structure, surface morphology, permeation and selectivity. This method represents a future-oriented green alternative to known industrial processes. © 2020, The Author(s)