Enhanced CO2 fixation in the biocatalytic carboxylation of resorcinol: Utilization of amines for amine scrubbing and in situ product precipitation

Ohde, Daniel; Thomas, Benjamin; Bubenheim, Paul; Liese, Andreas

doi:10.1016/j.bej.2020.107825

Cited by 9 publications

(21 citation statements)

References 34 publications

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“…Combining tetrabutylammonium bromide as precipitation agent, together with trimethylamine for CO 2 sequestration, allowed increase the carboxylation yield of an 80 mM solution of resorcinol from 7% to 43%. However, elevated triethylamine concentrations also increased the solubility of the precipitated salts requiring further reaction optimization. , …”

Section: Enzymatic Carboxylation and Co2 Utilization Systemsmentioning

confidence: 99%

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Enzymatic Conversion of CO₂: From Natural to Artificial Utilization

et al. 2023

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Enzymatic carbon dioxide fixation is one of the most important metabolic reactions as it allows the capture of inorganic carbon from the atmosphere and its conversion into organic biomass. However, due to the often unfavorable thermodynamics and the difficulties associated with the utilization of CO2, a gaseous substrate that is found in comparatively low concentrations in the atmosphere, such reactions remain challenging for biotechnological applications. Nature has tackled these problems by evolution of dedicated CO2-fixing enzymes, i.e., carboxylases, and embedding them in complex metabolic pathways. Biotechnology employs such carboxylating and decarboxylating enzymes for the carboxylation of aromatic and aliphatic substrates either by embedding them into more complex reaction cascades or by shifting the reaction equilibrium via reaction engineering. This review aims to provide an overview of natural CO2-fixing enzymes and their mechanistic similarities. We also discuss biocatalytic applications of carboxylases and decarboxylases for the synthesis of valuable products and provide a separate summary of strategies to improve the efficiency of such processes. We briefly summarize natural CO2 fixation pathways, provide a roadmap for the design and implementation of artificial carbon fixation pathways, and highlight examples of biocatalytic cascades involving carboxylases. Additionally, we suggest that biochemical utilization of reduced CO2 derivates, such as formate or methanol, represents a suitable alternative to direct use of CO2 and provide several examples. Our discussion closes with a techno-economic perspective on enzymatic CO2 fixation and its potential to reduce CO2 emissions.

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Section: Enzymatic Carboxylation and Co2 Utilization Systemsmentioning

confidence: 99%

“…However, elevated triethylamine concentrations also increased the solubility of the precipitated salts requiring further reaction optimization. 257,258 3.3.3. Engineering of the Biocatalyst.…”

Section: Reaction Engineering Of Enzymatic Carboxylation Reactionsmentioning

confidence: 99%

Enzymatic Conversion of CO₂: From Natural to Artificial Utilization

et al. 2023

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“…This approach is applied to calculate theoretical concentrations of CO 2 /H 2 CO 3 , HCO 3 − and CO 3 2− in aqueous TEA for the investigated pressure range. In combination with the equilibrium constant, determined in a previous work [10], theoretical equilibrium yields were calculated and compared with experimental reaction yields, as shown in Figure 2. At 100 kPa, predicted and experimental equilibrium yields fit well.…”

Section: Carboxylation At Elevated Co 2 Pressurementioning

confidence: 99%

“…Under ambient conditions (30 • C, atmospheric pressure), quaternary ammonium salts such as tetrabutylammonium (TBA) salts are reported to enhance the conversion of the enzymatic carboxylation of hydroxylated benzenes [15,16]. This effect was also reported to work in the aqueous TEA system; however, at greatly reduced efficiency [10]. This approach has now been tested at elevated CO 2 pressure to see if pressure has a positive effect on the reaction yield.…”

Section: Precipitation At Elevated Co 2 Pressurementioning

confidence: 99%

“…Recently, we showed that aqueous triethanolamine can be loaded very efficiently with gaseous CO 2 by using microbubble sparging in a bubble column setup [ 9 ]. Moreover, we discovered that the equilibrium yield depends on the HCO 3 − species, which was the main species of the dissolved inorganic carbon (DIC) content [ 10 ]. Similarly, Fan et al have recently shown that the carboxylation of catechol by a 2,3-dihydroxybenzoic acid decarboxylase from Aspergillus oryzae depends on the aqueous CO 2 concentration, with a high concentration of HCO 3 − being required under alkaline conditions [ 11 ].…”

Section: Introductionmentioning

confidence: 99%

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Enzymatic Carboxylation of Resorcinol in Aqueous Triethanolamine at Elevated CO2 Pressure

Ohde,

Thomas,

Bubenheim

et al. 2023

Molecules

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The fixation of CO2 by enzymatic carboxylation for production of valuable carboxylic acids is one way to recycle carbon. Unfortunately, this type of reaction is limited by an unfavourable thermodynamic equilibrium. An excess of the C1 substrate is required to increase conversions. Solvents with a high CO2 solubility, such as amines, can provide the C1 substrate in excess. Here, we report on the effect of CO2 pressures up to 1100 kPa on the enzymatic carboxylation of resorcinol in aqueous triethanolamine. Equilibrium yields correlate to the bicarbonate concentration. However, inhibition is observed at elevated pressure, severely reducing the enzyme activity. The reaction yields were reduced at higher pressures, whereas at ambient pressure, higher yields were achieved. Overall, CO2 pressures above 100 kPa have been demonstrated to be counterproductive for improving the biotransformation, as productivity decreases rapidly for only a modest improvement in conversion. It is expected that CO2 carbamylation intensifies at elevated CO2 pressures, causing the inhibition of the enzyme. To further increase the reaction yield, the in situ product precipitation is tested by the addition of the quaternary ammonium salt tetrabutylammonium bromide.

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