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Andrada Thesis Cover V04.Indd 1 17/10/2018 22:41 NITROGEN CONTAINING NITROGEN CONTAINING BIOBASED CHEMICALS BIOBASED BIOBASED CHEMICALS PRODUCED USING PRODUCED USING ENZYMES ENZYMES Andrada But Andrada But 2018 Andrada Thesis cover v04.indd 1 17/10/2018 22:41 Propositions 1. The expected similar reactivity of acidic amino acids based on identical functionalities is not in agreement with oxidative decarboxylation. (this thesis) 2. Iterative combination of economic and sustainability analysis with experimental data in an early stage, directs the focus for future research towards up- and down-stream the oxidative decarboxylation reaction. (this thesis) 3. Sustainability practices for all human activities make ethical concerns redundant. 4. Research that shows how climate change affects personal life, is essential to persuade the general public of the unforeseen effects of using fossil resources. 5. Since impalement is outdated, Dutch bureaucracy can complement education in the fight against corruption. 6. Gardening is an underestimated therapy for chronic diseases. Proposition belonging to the thesis, entitled: Nitrogen containing Biobased Chemicals produced using Enzymes Andrada But Wageningen, 10 December 2018 NITROGEN CONTAINING BIOBASED CHEMICALS PRODUCED USING ENZYMES Andrada But Andrada Thesis cover v05.indd 3 04/11/2018 21:03 Nitrogen Containing Biobased Chemicals produced using Enzymes Andrada But Thesis committee Promotor Prof. Dr J.P.M. Sanders Emeritus professor of Valorisation of Plant Production Chains Wageningen University & Research Co-promotor Dr E.L. Scott Associate professor, Biobased Chemistry and Technology Group Thesis Wageningen University & Research submitted in fulfilment of the requirements for the degree of doctor at Wageningen University Other members by the authority of the Rector Magnificus, Prof. Dr W.J.H. van Berkel, Wageningen University & Research Prof. Dr A.P.J. Mol, Dr F. Hollmann, Delft University of Technology in the presence of the Dr L. Claes, Catholic University of Leuven, Belgium Thesis Committee appointed by the Academic Board Dr J.A. Posada, Delft University of Technology to be defended in public on Monday 10 December 2018 This research was conducted under the auspices of the Graduate School VLAG (Advanced at 11 a.m. in the Aula. studies in Food Technology, Agrobiotechnology, Nutrition and Health Sciences). Andrada Thesis cover v05.indd 4 04/11/2018 21:03 NITROGEN NitrogenCONTAININGContaining BIOBASED CHEMICALS PRODUCED USING BiobasedENZYMES Chemicals produced using Enzymes Andrada But Andrada But Thesis committee Promotor Prof. Dr J.P.M. Sanders Emeritus professor of Valorisation of Plant Production Chains Wageningen University & Research Co-promotor Dr E.L. Scott Associate professor, Biobased Chemistry and Technology Group Thesis Wageningen University & Research submitted in fulfilment of the requirements for the degree of doctor at Wageningen University Other members by the authority of the Rector Magnificus, Prof. Dr W.J.H. van Berkel, Wageningen University & Research Prof. Dr A.P.J. Mol, Dr F. Hollmann, Delft University of Technology in the presence of the Dr L. Claes, Catholic University of Leuven, Belgium Thesis Committee appointed by the Academic Board Dr J.A. Posada, Delft University of Technology to be defended in public on Monday 10 December 2018 This research was conducted under the auspices of the Graduate School VLAG (Advanced at 11 a.m. in the Aula. studies in Food Technology, Agrobiotechnology, Nutrition and Health Sciences). Andrada Thesis cover v05.indd 5 04/11/2018 21:03 Andrada But Nitrogen Containing Biobased Chemicals produced using Enzymes, 152 pages. PhD thesis, Wageningen University, Wageningen, the Netherlands (2018) With references, with summary in English ISBN: 978-94-6343-490-4 DOI: http://doi.org/10.18174/45720 7 Andrada Thesis cover v05.indd 6 04/11/2018 21:03 Table of Contents Abbreviation list ................................................................................................................. 7 Chapter 1 Introduction ................................................................................................... 9 Chapter 2 Unusual differences in the reactivity of glutamic and aspartic acid in oxidative decarboxylation reactions .......................................................... 31 Chapter 3 The effect of side chain length and functionality of amino acids on the oxidative decarboxylation reaction ........................................................... 49 Chapter 4 Enzymatic halogenation and oxidation using an alcohol oxidase-vanadium chloroperoxidase cascade .......................................................................... 65 Chapter 5 Techno-economic assessment of the production of biobased nitriles from glutamic acid ............................................................................................... 83 Chapter 6 General discussion...................................................................................... 103 References ……………………………………………………………………………..117 Appendices ……………………………………………………………………………..123 Appendix A. Supplementary information to Chapter 2 ............................................. 124 Appendix B. Supplementary information to Chapter 3 .............................................. 127 Appendix C. Supplementary information to Chapter 4 ............................................. 129 Appendix D. Supplementary information to Chapter 5 ............................................. 131 Summary …………………………………………………………………………….139 Acknowledgements ........................................................................................................ 143 About the author ............................................................................................................. 147 Abbreviation list AA Amino acid hSer homoSerine Aaa α-aminoadipic acid hSerCN Hydroxypropionitrile AaaCN 4-cyanobutanoic acid Km Michaelis constant Aba α-aminobutanoic acid Maa β-methyl aspartic acid AbaCN propionitrile MCD Monochlorodimedone ABTS 2,2′-azino-bis(3-ethylbenzo Me, -CH3 Methyl group thiazoline-6-sulfonic acid) MeAsp Aspartic acid β-methyl ester AOX Alcohol oxidase MeAspCN Methyl 2-cyanoacetate Asp Aspartic acid MeGlu Glutamic acid γ-methyl ester AspCN 2-cyanopropanoic acid MeGluCN Methyl 3-cyanopropanoate Br Bromine N Nitrogen C Carbon Na Sodium ca. circa NaBr Sodium bromide Cl Chlorine NaCl Sodium chloride CN Nitrile, nitrile functionality NaOCl Sodium hypochlorite, bleach CO2 Carbon dioxide nLeu norLeucine -COOH Carboxyl, acid functionality nLeuCN Valeronitrile -COOMe Methyl ester functionality nVal norValine CPO Chloroperoxidase (Fe-Heme nValCN Butyronitrile cofactor) O Oxygen DDGS distiller’s dried grains with -OH Hydroxyl functionality solubles Phe Phenylalanine FAD Flavin adenine dinucleotide Ru Ruthenium FDCA 2,5-furandicarboxylic acid Ser Serine GHG Greenhouse gasses SerCN Glycolonitrile, Hydroxyacetonitrile Glu Glutamic acid Tris Tris(hydoxymethyl)aminomethane GluCN 3-cyanopropanoic acid V Vanadium GOX Glucose oxidase Val Valine H Hydrogen ValCN Isobutyronitrile H2O2 Hydrogen peroxide VCPO Vanadium chloroperoxidase H2SO4 Sulphuric acid VHPOs Vanadium haloperoxidases HCN Hydrogen cyanide W Tungsten HOBr Hypobromous acid wt-% Weight percentage HOCl Hypochlorous acid X Halogens (Cl, Br) HOX Hypohalous acid X+ Halogenating species HPLC High performance liquid chromatography HPO Haloperoxidase HRP Horseradish peroxidase Chapter 1 Introduction Chapter 1 Modern society is highly dependent on commodity products such as plastics, fuels and medicines. Plastics, for example, are waterproof, lightweight, durable and hygienic, and successfully replace materials such as metal and wood. The plastic bag, the drinks bottle, food packaging, the computer and plastic toys (Figure 1.1) are a few examples of everyday plastic containing items, widely used in the modern world. Figure 1.1. Examples of plastic items. Despite their benefits, the excessive use of plastics creates serious issues on our ecosystem.1 For example, the lightweight plastics, such as the single-use bags, are creating severe waste management issues and environmental pollution. Today, phasing-out measures of the lightweight plastics are being taken around the world.2 Without doubt, on short term these measures are reducing the amount of single-use plastics to a certain extent. On the long term, it creates awareness among the users,3 and it allows the development and marketing of alternatives such as compostable plastics.4 However, behind the scenes issues related to plastics, and to chemicals in general, are not solved by the phasing-out measures. These behind the scenes issues relate to the way chemicals are produced. While the use of chemicals facilitates and simplifies our lives, their production from fossil resources and their use have unforeseen consequences such as pollution, geo- political tensions, and climate change.5 10 Introduction From fossil resources to climate change Nowadays, the production of chemicals (such as plastics) relies mainly on fossil feedstocks and its use changed the modern world as we know it. The exploitation and use of fossil feedstocks as direct products (e.g. kerosene) or conversion into other chemicals (e.g. plastics) generates high amounts of greenhouse gasses (GHG) such as CO2, CH4 and NOX. The global concentration of CO2 rose from 340 ppm to 405 ppm over the period 1980 to 2017 which translates to a rise of the average global temperature of about 0.7°C.6 This effect is called global warming and the main cause of it is attributed to anthropogenic
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