Design and exploitation of cadaverine metabolic pathway for simple N-heterocyclic chemical production.

Nitrogen-heterocycles are widely found in nature as subunits of compounds from secondary metabolism (vitamins, alkaloids, hormones etc.) and are valuable building blocks to manufacture a wide range of pharmaceuticals, agrochemicals, flavours and fragrances. Currently, N-heterocycles are produced thr...

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Main Author: Anyanwu, Valentine E.
Format: Thesis (University of Nottingham only)
Language:English
Published: 2019
Subjects:
Online Access:https://eprints.nottingham.ac.uk/56093/
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author Anyanwu, Valentine E.
author_facet Anyanwu, Valentine E.
author_sort Anyanwu, Valentine E.
building Nottingham Research Data Repository
collection Online Access
description Nitrogen-heterocycles are widely found in nature as subunits of compounds from secondary metabolism (vitamins, alkaloids, hormones etc.) and are valuable building blocks to manufacture a wide range of pharmaceuticals, agrochemicals, flavours and fragrances. Currently, N-heterocycles are produced through unsustainable chemical processes that rely on petrochemical feedstocks and high-energy consumption. The six-membered simple N-heterocycle Δ¹-piperideine (2,3,4,5-tetrahydropyridine), is a key building block for biosynthesis of some alkaloids, for example, the piperidine, quinolizidine, indolizidine and lycopodium alkaloids. Δ¹-piperideine also has considerable promise as a platform compound for chemical synthesis of functionalized or complex compounds with economic importance. Although the bioproduction of complex, functionalised N-heterocycles have been reported, bioproduction of unsubstituted simple N-heterocycles have not yet been achieved. Advances in metabolic engineering and synthetic biology offers an approach to develop bioprocesses for sustainable production of simple N-heterocycles from renewable sugar feedstocks. Δ¹-Piperideine can be obtained by oxidation of cadaverine using amine oxidases or transaminases, to yield 5-aminopentanal. This product is known to cyclise spontaneously into Δ¹-piperideine. However, Δ¹-piperideine reacts spontaneously in aqueous solution to form the multimeric products (tetrahydroanabasine, α-tripiperideine and isotripiperideine). Therefore, the suitability of putrescine oxidase from Rhodococcus erythropolis (PuORh) for cell-free and whole-cell bioproduction of Δ¹-piperideine was studied. PuORh was characterised for the first time by monitoring oxygen concentration in a direct substrate consumption assay. Using purified PuORh and PuORh induced whole cells; the conversion of cadaverine to Δ¹-piperideine was demonstrated qualitatively and quantitatively. This study indicates that PuORh is suitable for the bioproduction of Δ¹-piperideine. Finally, a metabolic route has been designed and proposed for whole cell bioproduction of Δ¹-Piperideine from renewable feedstocks.
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spelling nottingham-560932025-02-28T14:24:07Z https://eprints.nottingham.ac.uk/56093/ Design and exploitation of cadaverine metabolic pathway for simple N-heterocyclic chemical production. Anyanwu, Valentine E. Nitrogen-heterocycles are widely found in nature as subunits of compounds from secondary metabolism (vitamins, alkaloids, hormones etc.) and are valuable building blocks to manufacture a wide range of pharmaceuticals, agrochemicals, flavours and fragrances. Currently, N-heterocycles are produced through unsustainable chemical processes that rely on petrochemical feedstocks and high-energy consumption. The six-membered simple N-heterocycle Δ¹-piperideine (2,3,4,5-tetrahydropyridine), is a key building block for biosynthesis of some alkaloids, for example, the piperidine, quinolizidine, indolizidine and lycopodium alkaloids. Δ¹-piperideine also has considerable promise as a platform compound for chemical synthesis of functionalized or complex compounds with economic importance. Although the bioproduction of complex, functionalised N-heterocycles have been reported, bioproduction of unsubstituted simple N-heterocycles have not yet been achieved. Advances in metabolic engineering and synthetic biology offers an approach to develop bioprocesses for sustainable production of simple N-heterocycles from renewable sugar feedstocks. Δ¹-Piperideine can be obtained by oxidation of cadaverine using amine oxidases or transaminases, to yield 5-aminopentanal. This product is known to cyclise spontaneously into Δ¹-piperideine. However, Δ¹-piperideine reacts spontaneously in aqueous solution to form the multimeric products (tetrahydroanabasine, α-tripiperideine and isotripiperideine). Therefore, the suitability of putrescine oxidase from Rhodococcus erythropolis (PuORh) for cell-free and whole-cell bioproduction of Δ¹-piperideine was studied. PuORh was characterised for the first time by monitoring oxygen concentration in a direct substrate consumption assay. Using purified PuORh and PuORh induced whole cells; the conversion of cadaverine to Δ¹-piperideine was demonstrated qualitatively and quantitatively. This study indicates that PuORh is suitable for the bioproduction of Δ¹-piperideine. Finally, a metabolic route has been designed and proposed for whole cell bioproduction of Δ¹-Piperideine from renewable feedstocks. 2019-07-18 Thesis (University of Nottingham only) NonPeerReviewed application/pdf en arr https://eprints.nottingham.ac.uk/56093/1/Anyanwu%20Valentine-Final%20Thesis%20after%20Correction.pdf Anyanwu, Valentine E. (2019) Design and exploitation of cadaverine metabolic pathway for simple N-heterocyclic chemical production. PhD thesis, University of Nottingham. Biotechnology sustainability metabolic engineering cadaverine Δ¹-piperideine N-heterocycles putrescine oxidase biocatalysis bioproduction
spellingShingle Biotechnology
sustainability
metabolic engineering
cadaverine
Δ¹-piperideine
N-heterocycles
putrescine oxidase
biocatalysis
bioproduction
Anyanwu, Valentine E.
Design and exploitation of cadaverine metabolic pathway for simple N-heterocyclic chemical production.
title Design and exploitation of cadaverine metabolic pathway for simple N-heterocyclic chemical production.
title_full Design and exploitation of cadaverine metabolic pathway for simple N-heterocyclic chemical production.
title_fullStr Design and exploitation of cadaverine metabolic pathway for simple N-heterocyclic chemical production.
title_full_unstemmed Design and exploitation of cadaverine metabolic pathway for simple N-heterocyclic chemical production.
title_short Design and exploitation of cadaverine metabolic pathway for simple N-heterocyclic chemical production.
title_sort design and exploitation of cadaverine metabolic pathway for simple n-heterocyclic chemical production.
topic Biotechnology
sustainability
metabolic engineering
cadaverine
Δ¹-piperideine
N-heterocycles
putrescine oxidase
biocatalysis
bioproduction
url https://eprints.nottingham.ac.uk/56093/