Project

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Environmental photochemistry of amino acid-based biomolecules

English title Environmental photochemistry of amino acid-based biomolecules
Applicant McNeill Kristopher
Number 159809
Funding scheme Project funding (Div. I-III)
Research institution Institut für Biogeochemie und Schadstoffdynamik ETH Zürich
Institution of higher education ETH Zurich - ETHZ
Main discipline Geochemistry
Start/End 01.07.2015 - 30.09.2019
Approved amount 571'739.00
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All Disciplines (3)

Discipline
Geochemistry
Other disciplines of Environmental Sciences
Other disciplines of Earth Sciences

Keywords (10)

natural organic matter; hydrogen peroxide; indirect photolysis; hydroxyl radical; amino acids; singlet oxygen; direct phototransformation; proteins; photochemistry; reactive oxygen species

Lay Summary (German)

Lead
Biomoleküle bestehend aus Aminosäuren sind zentrale Bausteine des Lebens und spielen eine entscheidende Rolle in biogeochemischen Prozessen in der Umwelt. In Oberflächengewässern sind Aminosäuren verschiedenen Abbauprozessen ausgesetzt und können zum Beispiel von photochemisch-produzierten reaktiven Sauerstoffmolekülen oxidiert werden. Obwohl photochemische Abbauprozesse von Proteinen Peptiden und Aminosäuren eine zentrale Rolle in der Umwelt spielen wurden bisher nur wenige systematische Studien zu diesem Thema durchgeführt.
Lay summary

Inhalt und Ziel des Forschungsprojekts

Unser Ziel ist es Wissenslücken in der umweltrelevanten Photochemie von Biomolekülen zu schliessen. Im Detail werden wir (1) die Photochemie von Cysteine und Cystine in freier Lösung charakterisieren; (2) die Photochemie von ausgewählten Aminosäuren in nicht-ribosomalen Peptiden (NRPs) und ribosomal synthetisierten und posttranslational modifizierten Peptiden (RiPPs) unter umweltrelevanten Bedingungen erarbeiten; (3) den Einfluss von gebundenem Zink auf die Photochemie von Histidin und Cystein untersuchen; und (4) die Inaktivierung von extrazellulären Enzymen in Zusammenhang mit spezifischer Oxidierung einzelner Aminosäuren bringen. Jedes dieser vier Ziele stellt momentan eine Wissenslücke im Bereich des photochemischen Abbauverhalten von Biomolekülen dar. Wir warden einheitliche Methoden für die photochemischen Untersuchungen verwenden, so dass die Weiterenticklung von einem Projektteil auch gleichzeitig einen Fortschritt für die anderen Ziele bewirkt - z.B. der Übergang von Cysteine Photochemie zu Cysteine-Zink Komplexen und Metall-Cofaktoren in Enzymen. 

Wissenschaftlicher und gesellschaftlicher Kontext des Forschungsprojekts

 Unsere Arbeit wird neue und wichtige Informationen über den photochemischen Abbau von Biomolekülen auf der molekularen Ebene generieren. Die Ergenisse werden unser Verständis von (i) Nährstoffkreisläufen, (ii) Abbau von Peptid-basierten Schadstoffen, (iii) enzymatischen Abbauprozessen, und (iv) Analytik von Biomakromolekülen in der Umwelt verbessern.  Dieses Projekt wird die Aus- und Weiterbildung von drei Doktoranden und Masterarbeiten von sechs Studenten fördern.  

 

 

Direct link to Lay Summary Last update: 29.05.2015

Responsible applicant and co-applicants

Employees

Publications

Publication
Singlet Oxygen Photooxidation of Peptidic Oxazoles and Thiazoles
Manfrin Alessandro, Borduas-Dedekind Nadine, Lau Kate, McNeill Kristopher (2019), Singlet Oxygen Photooxidation of Peptidic Oxazoles and Thiazoles, in The Journal of Organic Chemistry, 84(5), 2439-2447.
Proteomics Approach To Trace Site-Specific Damage in Aquatic Extracellular Enzymes During Photoinactivation
Egli Christine M., Janssen Elisabeth M.-L. (2018), Proteomics Approach To Trace Site-Specific Damage in Aquatic Extracellular Enzymes During Photoinactivation, in Environmental Science & Technology, 52(14), 7671-7679.
Aquatic indirect photochemical transformations of natural peptidic thiols: impact of thiol properties, solution pH, solution salinity and metal ions
Chu Chiheng, Stamatelatos Dimitrios, McNeill Kristopher (2017), Aquatic indirect photochemical transformations of natural peptidic thiols: impact of thiol properties, solution pH, solution salinity and metal ions, in Environmental Science: Processes & Impacts, 19, 1518-1527.
Photochemical and Nonphotochemical Transformations of Cysteine with Dissolved Organic Matter
Chu Chiheng, Erickson Paul R., Lundeen Rachel A., Stamatelatos Dimitrios, Alaimo Peter J., Latch Douglas E., McNeill Kristopher (2016), Photochemical and Nonphotochemical Transformations of Cysteine with Dissolved Organic Matter, in Environmental Science & Technology, 50(12), 6363-6373.
Photooxidation of the Antimicrobial, Nonribosomal Peptide Bacitracin A by Singlet Oxygen under Environmentally Relevant Conditions
Lundeen Rachel, Chu Chiheng, Sander Michael, McNeill Kristopher (2016), Photooxidation of the Antimicrobial, Nonribosomal Peptide Bacitracin A by Singlet Oxygen under Environmentally Relevant Conditions, in Environmental Science & Technology, 50(16), 8586-8595.
Assessing the Indirect Photochemical Transformation of Dissolved Combined Amino Acids through the Use of Systematically Designed Histidine-Containing Oligopeptides
Chu Chiheng, Lundeen Rachel, Sander Michael, McNeill Kristopher (2015), Assessing the Indirect Photochemical Transformation of Dissolved Combined Amino Acids through the Use of Systematically Designed Histidine-Containing Oligopeptides, in Environmental Science & Technology, 49(21), 12798-12807.

Scientific events

Active participation

Title Type of contribution Title of article or contribution Date Place Persons involved
CH Analysis Talk given at a conference Analysis of singlet oxygen-induced transformation products in aquatic extracellular enzymes 11.04.2019 Beatenberg, Switzerland Egli Christine Maria; Janssen Elisabeth Marie-Louise;
Anakon 2019 Talk given at a conference Proteomics techniques to map molecular damage within aquatic extracellular enzymes 25.03.2019 Münster, Germany Egli Christine Maria; Janssen Elisabeth Marie-Louise;
Gorden Research Seminar, Environmental Science: Water Talk given at a conference Mapping photochemical modifications of amino acids in aquatic extracellular enzymes 24.06.2018 Holderness, United States of America Janssen Elisabeth Marie-Louise; Egli Christine Maria;
Gordon Research Conference, Environmental Science: Water Poster Mapping photochemical modifications of amino acids in aquatic extracellular enzymes 24.06.2018 Holderness, United States of America Janssen Elisabeth Marie-Louise; Egli Christine Maria;
Swiss Society of Mass Spectrometry (SGMS) Talk given at a conference Spatiotemporal Damage of Enzymes Resolved by Proteomic Techniques 25.10.2017 Beatenberg, Switzerland Janssen Elisabeth Marie-Louise; Egli Christine Maria;
Swiss Chemical Society Conference Talk given at a conference Stability of Extracellular Enzymes in Surface Waters. 21.08.2017 Bern, Switzerland Janssen Elisabeth Marie-Louise; Egli Christine Maria;
253rd American Chemical Society National Meeting Talk given at a conference Photochemical damage of extracellular enzymes. 02.08.2017 San Francisco, United States of America Egli Christine Maria; Janssen Elisabeth Marie-Louise;
Seminar Series in Civil Engineering and Geosciences Dept. Individual talk Environmental Stability of Bioactive Macromolecule. 15.07.2017 Newcastle, Great Britain and Northern Ireland Egli Christine Maria; Janssen Elisabeth Marie-Louise;
16th International ICCE Conference Talk given at a conference Stabillity of extracellular enzyme in surface waters: Comprehensive structural and functional analysis by proteomics techniques and enzymology 17.06.2017 Oslo, Norway Janssen Elisabeth Marie-Louise; Egli Christine Maria;
5th Enzymes in The Environment Conference Poster Site-specific damage and inactivation of extracellular enzymes in the aquatic environment. 24.07.2016 Bangor, Great Britain and Northern Ireland Janssen Elisabeth Marie-Louise; Egli Christine Maria;
Gordon Research Conference, Environmental Sciences: Water Talk given at a conference Site-specific damage and inactivation of extracellular enzymes in the aquatic environment. 26.06.2016 Holderness, United States of America Janssen Elisabeth Marie-Louise; Egli Christine Maria;
Seminar Series, Department of Chemistry, University of Padova Individual talk Environmental Phototransformation processes of pollutants and biomolecules. 22.04.2016 Padova, Italy Janssen Elisabeth Marie-Louise; Egli Christine Maria;
251st American Chemical Society National Meeting Talk given at a conference Photoinactivation of aquatic extracellular enzymes in the aquatic environment. 13.03.2016 San Diego, United States of America Janssen Elisabeth Marie-Louise; Egli Christine Maria;


Awards

Title Year
Environmental Science and Technology Journal - Young Investigator Recognition 2019
Travel Award by Swiss Group for Mass Spectrometry (SGMS) 2018

Associated projects

Number Title Start Funding scheme
138008 Environmental photochemistry of amino acids, peptides and proteins 01.01.2012 Project funding (Div. I-III)
138008 Environmental photochemistry of amino acids, peptides and proteins 01.01.2012 Project funding (Div. I-III)

Abstract

Amino acid-based biomolecules are central building blocks of life and of key importance in the biogeochemistry of aquatic systems. In these systems, amino acids are susceptible to oxidation by photochemically generated reactive oxygen species. Despite the importance of environmental photochemical degradation of proteins, peptides and amino acids, there remain few systematic studies on this topic. This proposal aims to fill gaps in our knowledge regarding the environmental photochemistry of amino acid-based biomolecules in aquatic systems.The specific objectives of this proposal are to (1) Characterize the photochemistry of freely dissolved cysteine and cystine; (2) To delineate the environmental photochemistry of selected amino acids found in non-ribosomal peptides (NRPs) and ribosomally synthesized and posttranslationally modified peptides (RiPPs); (3) To determine the effect of zinc binding on the photooxidation of histidine and cysteine; and, (4) To assess photoinactivation of extracellular enzymes in relation to site-specific oxidation of AA residues. These objectives each represent current blind spots in our understanding of the photochemical fate of amino acid-based biomolecules. They also share unifying methodological concepts for the photochemical procedures and analysis and are interconnected as advancements in one project area will facilitate our studies on the others (e.g. going from cysteine photochemistry over Cys-zinc complexes to (metallo-)enzyme photoinactivation). The work plan is organized into four Subprojects that will be carried out by three starting PhD students (3 x 3 years) and a senior PhD student (1 year). The expected scientific outcome is an improved understanding of amino acid photooxidation in surface waters at the molecular level. Specifically, this project will illuminate important areas of the environmental chemistry of amino acids that have mostly been ignored, including the wide-open area of non-canonical NRP and RiPP amino acids, metal-amino acid complexes, and intact enzymes in natural water samples. This understanding promises to impact the larger scientific community, including biogeochemists studying sulfur and nitrogen element cycling, environmental chemists looking at peptide-based water contaminants, and ecologists interested in the role of extracellular enzymes in nutrient acquisition. In addition, we expect to make methodological advances that will aid in the study of enzymes and other biomacromolecules in natural waters in the future. The proposed project will also achieve education outcomes including four PhD students and six related master thesis students. Numerous synergisms are expected to arise from the parallel projects on distinct yet closely related topics.
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