Whole‐Cell Photoenzymatic Cascades to Synthesize Long‐Chain Aliphatic Amines and Esters from Renewable Fatty Acids

Abstract

Long-chain aliphatic amines such as (S,Z)-heptadec-9-en-7-amine and 9-aminoheptadecane were synthesized from ricinoleic acid and oleic acid, respectively,b ywhole-cell cascade reactions using the combination of an alcohol dehydrogenase (ADH) from Micrococcus luteus,a ne ngineered amine transaminase from Vibrio fluvialis (Vf-ATA), and ap hotoactivated decarboxylase from Chlorella variabilis NC64A (Cv-FAP) in aone-pot process.Inaddition, long chain aliphatic esters such as 10-(heptanoyloxy)dec-8-ene and octylnonanoate were prepared from ricinoleic acid and oleic acid, respectively,byusing the combination of the ADH, aBaeyer-Villiger monooxygenase variant from Pseudomonas putida KT2440, and the Cv-FAP.T he target compounds were produced at rates of up to 37 Ug À1 dry cells with conversions up to 90 %. Therefore,this study contributes to the preparation of industrially relevant long-chain aliphatic chiral amines and esters from renewable fatty acid resources.

Rational Engineering of a Multi‐Step Biocatalytic Cascade for the Conversion of Cyclohexane to Polycaprolactone Monomers in Pseudomonas taiwanensis

“…[ 1 ] Multi‐step biocatalysis employing whole cells emerged as a powerful tool for the synthesis of value‐added compounds. [ 2–4,5 ] Precise and delicate fine‐tuning of gene expression is required to balance individual enzyme amounts and activities for the construction of “designer cells.” [ 1,6,7,8 ] Especially “artificial cascades” employing heterologous genes of diverse origin constitute a major challenge as they introduce novel enzymatic functions into the host. [ 4,9 ] On the one hand, it is crucial to provide sufficient enzyme amounts to sustain reasonable rates.…”

Carboxylic Acid Reductase Can Catalyze Ester Synthesis in Aqueous Environments

“…[4] As biocatalysis by enzymes or metabolically engineered cells are generally accepted as sustainable means for production of fine chemicals in the future, the identification of new enzymatic reactions to catalyze esterification in aqueous environments will pave the way for performing esterification with metabolically engineered cells. [5] Up until now, reports of efficient enzymatic esterification reactions in aqueous environments are limited. [6] For examples, although non-ribosomal peptide synthetase (NRPS) can catalyze esterification and amidation, the use of NRPS as a biocatalyst is challenging, as NRPS reactions are substrate-specific and require a defined reaction order, thus, limiting the range of convertible carboxylic acids.…”

Production of Bio-alkanes from Biomass and CO2

“…Furthermore, our proposed cascading circular system is a flexible interdisciplinary platform and the general concept of combining microbial, electrochemical, and photocatalysis has opened a whole new research frontier, which can be expanded and diversified with tailored designs with respect to feedstocks, intermediates, and targeted products. For example, in addition to producing alkanes, the produced intermediated carboxylic acids can be valorised to terminal alkenes, fatty amines, and alcohols, which are very important compounds in the field of polymers and surfactants [38,46,47].…”