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Trichoderma Reesei Toni Paasikallio, Anne Huuskonen and Marilyn G Paasikallio et al. Microb Cell Fact (2017) 16:119 DOI 10.1186/s12934-017-0736-3 Microbial Cell Factories RESEARCH Open Access Scaling up and scaling down the production of galactaric acid from pectin using Trichoderma reesei Toni Paasikallio, Anne Huuskonen and Marilyn G. Wiebe* Abstract Background: Bioconversion of D-galacturonic acid to galactaric (mucic) acid has previously been carried out in small scale (50–1000 mL) cultures, which produce tens of grams of galactaric acid. To obtain larger amounts of biologically produced galactaric acid, the process needed to be scaled up using a readily available technical substrate. Food grade pectin was selected as a readily available source of D-galacturonic acid for conversion to galactaric acid. Results: We demonstrated that the process using Trichoderma reesei QM6a Δgar1 udh can be scaled up from 1 L to 1 10 and 250 L, replacing pure D-galacturonic acid with commercially available pectin. T. reesei produced 18 g L− galac- 1 1 taric acid from food-grade pectin (yield 1.00 g [g D-galacturonate ­consumed]− ) when grown at 1 L scale, 21 g L− 1 1 galactaric acid (yield 1.11 g [g D-galacturonate ­consumed]− ) when grown at 10 L scale and 14 g L− galactaric acid 1 (yield 0.77 g [g D-galacturonate ­consumed]− ) when grown at 250 L scale. Initial production rates were similar to those observed in 500 mL cultures with pure D-galacturonate as substrate. Approximately 2.8 kg galactaric acid was precipitated from the 250 L culture, representing a recovery of 77% of the galactaric acid in the supernatant. In addi- tion to scaling up, we also demonstrated that the process could be scaled down to 4 mL for screening of production strains in 24-well plate format. Production of galactaric acid from pectin was assessed for three strains expressing 1 uronate dehydrogenase under alternative promoters and up to 11 g L− galactaric acid were produced in the batch process. Conclusions: The process of producing galactaric acid by bioconversion with T. reesei was demonstrated to be equally efcient using pectin as it was with D-galacturonic acid. The 24-well plate batch process will be useful screen- ing new constructs, but cannot replace process optimisation in bioreactors. Scaling up to 250 L demonstrated good reproducibility with the smaller scale but there was a loss in yield at 250 L which indicated that total biomass extrac- tion and more efcient DSP would both be needed for a large scale process. Keywords: Galactaric acid, Mucic acid, D-Galacturonic acid, Pectin, Trichoderma reesei, Scale-up, Scale-down Background acid, furandicarboxylic acid (which is being developed Tere is considerable interest in replacing chemicals as a substitute for terephthalic acid) and other platform derived from petroleum with bio-derived chemicals, i.e. chemicals, including anhydrides, diesters and diallyls chemicals obtained by bioconversion and/or chemical which can be used in the synthesis of higher value prod- conversion from renewable biological resources, primar- ucts [1–3]. Both compounds can be prepared by nitric ily plants. Both galactaric and glucaric acids have been acid oxidation of the corresponding monosaccharide identifed as substrates for chemical conversion to adipic (d-glucose or d-galactose) [4]. Although biotechnologi- cal conversions may be preferable to nitric acid oxida- tion, biotechnological conversion of d-glucose to glucaric *Correspondence: [email protected] acid continues to be challenging [5]. However, galactaric VTT Technical Research Centre of Finland Ltd., P.O. Box 1000, 02044 Espoo, Finland acid has been produced from d-galacturonic acid using © The Author(s) 2017. This article is distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The Creative Commons Public Domain Dedication waiver (http://creativecommons.org/ publicdomain/zero/1.0/) applies to the data made available in this article, unless otherwise stated. Paasikallio et al. Microb Cell Fact (2017) 16:119 Page 2 of 11 genetically modifed Escherichia coli and Trichoderma needed. T. reesei Δgar1 udh was used in scaling up the reesei at concentrations of 10 [6] to 20 [7] g L−1, which process since it has already been demonstrated to pro- are high enough concentrations for precipitation from duce up to 20 g L−1 galactaric acid from d-galacturonic the culture broth, making biotechnologically derived acid [7]. Since T. reesei does not hydrolyse pectin [9] galactaric acid available for assessment in further chemi- and to facilitate sterilisation of viscous pectin solutions, cal conversions [6]. Te genetically modifed E. coli or T. enzymatic pre-hydrolysis of the pectin was necessary. reesei convert d-galacturonic acid to galactaric acid by An alternative approach would be to develop a consoli- the action of a uronate dehydrogenase (UDH), which is dated process using a production strain such as Asper- expressed in a strain in which normal d-galacturonic acid gillus niger, which produces native pectinases. However, metabolism has been disrupted [6, 8]. In the case of T. A. niger can metabolise galactaric acid [8] and a strain in reesei, deletion of the gene encoding NADPH-dependent which this pathway has been disrupted has only recently d-galacturonate reductase (gar1), the frst step in the fun- become available [10]. A production process with A. niger gal pathway for d-galacturonic acid metabolism, is suf- has not yet been developed. fcient to disrupt the pathway and expression of the A. In addition to scaling up the process of producing tumefaciens udh gene results in a strain which produces galactaric acid to provide galactaric acid for chemical galactaric acid [8]. reactions, we were also interested in providing a scaled Although chemically produced galactaric acid is com- down process, which would enable the screening of new mercially available, biotechnologically produced galac- strains [11]. Galactaric acid production by T. reesei has taric acid will contain diferent impurities and the efect previously been demonstrated in fask cultures [8], but at of these on specifc chemical reactions needs to be much lower concentrations than can be obtained in bio- assessed to provide feedback on the purity requirements reactors [7]. Running and Bansal [12] demonstrated that and consequent implications for downstream processing 24-well plates can have as good or better oxygen trans- (DSP) in the biotechnological process. For this reason fer as shaken fasks, depending on the shaking regime it may be necessary to produce substantial quantities of applied, and 24-well plates are increasingly being used galactaric acid using biotechnology, even though the pro- for the cultivation of flamentous fungi [13–15]. It is cess is not ready for commercialisation. therefore useful to assess whether galactaric acid produc- Te substrate for biotechnological production of galac- tion by T. reesei could be scaled down for production in taric acid is d-galacturonic acid, which can be obtained 24-well plates using pectin as substrate. by hydrolysis of pectin. Zhang et al. [6] demonstrated In this paper we describe the production of galactaric that galactaric acid could be produced from enzymati- acid by T. reesei VTT D-161646 from enzyme hydrolysed cally hydrolysed sugar beet pulp, but noted that the yield pectin at 1, 10 and 250 L scales. We also demonstrate of galactaric acid on sugar beet pulp was relatively low that the process can be scaled down to 4 mL for strain (0.14 g galactaric acid per g sugar beet pulp), refecting screening, for example in considering the efectiveness of the high concentration of other compounds in the pulp, alternative promoters for expression of the uronate dehy- particularly d-glucose and l-arabinose. d-Galacturonic drogenase gene, as shown here. acid is currently available only at high prices (more than €3000 per kg) and is thus not suitable for producing kilo- Results gram amounts of galactaric acid for chemical testing. Scaling down production of galactaric acid in 24‑well However, food grade pectins are commercially available plates at prices in the range of €10–100 per kg, making them Tree transformants of T. reesei were generated in a reasonable source for preparation of large amounts of which the uronate dehydrogenase (udh) gene was galactaric acid. It should be noted that food grade pectin expressed under diferent promoters and these were may be diluted with additives such as sucrose or glucose. cultivated in 24-well plates to assess the suitability of Having received a request to provide a 2 kg sample of bio- the 24-well plate format for galactaric acid produc- technologically produced galactaric acid for use in chem- tion. All transformants which contained the udh gene ical reactions, we decided to use pectin as the source of produced galactaric acid in the 24-well plates. T. reesei d-galacturonic acid in scaling up the process of galactaric VTT D-161646 produced 8.8 g L−1 galactaric acid from acid production with T. reesei Δgar1 udh. An industrial 10.7 g d-galacturonic acid in 6 days and 10.5 g L−1 from process would be expected to use sugar beet pulp, cit- 20 g L−1 pectin (Sigma), hydrolysed to give 11.6 g L−1 rus waste and other pectin-rich waste streams or crude d-galacturonic acid, demonstrating that galactaric acid extractions of pectin from these sources, which would could be produced in the 24-well plates (Fig. 1; Table 1). not compete with the food use of current pectin pro- No galactaric acid was produced by M122, the control duction, but these were not readily available at the scale strain lacking udh, nor in wells which had not been Paasikallio et al.
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