Predicting the high concentration co-solvent influence on the reaction equilibria of the ADH-catalyzed reduction of acetophenone

Wangler, Anton; Loll, Rouven; Greinert, Thorsten; Sadowski, Gabriele; Held, Christoph

doi:10.1016/j.jct.2018.08.021

Cited by 20 publications

(21 citation statements)

References 38 publications

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“…The required pure-component ePC-SAFT parameters were taken from the literature (PEG, Na + , Citrate 3− , vitamins) or were estimated by fitting them to experimental densities and osmotic coefficients of binary water-Na 2 Tartrate systems (Tartrate 2− ). [32][33][34][35][36][37][38] The binary interaction parameters between phase formers (PEG, salt ions) were fitted to experimental tie-lines from the literature (PEG-Na 3 Citrate) or to data determined in this work (PEG-Na 2 Tartrate). 17 The partition coefficients of vitamins (VB2, VB3 acid , VB3 amide , VB9, VB12) were predicted using the activity coefficients obtained with ePC-SAFT in each phase and at different tie-line compositions.…”

Section: Introductionmentioning

confidence: 99%

“…In case of VB9, two species (VB9 2− , VB9 3− ) will be present at the conditions under investiga-Experimental results can be found in Tables S4 and S5 (SI). modeling approach from Reschke et al31 to the much simpler classical ePC-SAFT approach (homosegmented PEG, spherical Citrate 3− ) [32][33][34]. All parameters as well as the experimental ATPS data for this comparison were available in the literature for the LLE of the system water-PEG-Na 3 Citrate at 298.15 K and 1 bar.…”

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confidence: 99%

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Partitioning of water‐soluble vitamins in biodegradable aqueous two‐phase systems: Electrolyte perturbed‐chain statistical associating fluid theory predictions and experimental validation

et al. 2020

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Partition coefficients (K) of vitamins (riboflavin, nicotinic acid, nicotinamide, folic acid, cyanocobalamin) in aqueous two‐phase systems (ATPS) composed by polyethylene glycol (PEG 4000, PEG 6000) and organic salt (sodium citrate and sodium tartrate) at T = 298.15 K and p = 1 bar have been studied. Data on liquid–liquid equilibria of the ATPS considered in this study have been taken from the literature (PEG‐Na3Citrate) or measured in this work (PEG‐Na2Tartrate) for PEG 4000 and PEG 6000 at T = 298.15 K and p = 1 bar. The experimental K values were validated by electrolyte perturbed‐chain‐statistical associating fluid theory predictions. The neutral cyanocobalamin has the highest K values among all studied vitamins at any ATPS studied in this work. This finding contrasted with expectations based on literature data which let assume that charged species have typically the highest K values in the considered ATPS. Thus, besides the typically strong charge–charge interactions especially specific forces (e.g., hydrogen bonding) explains the strong PEG‐cyanocobalamin interaction resulting in the high K values.

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Section: Introductionmentioning

confidence: 99%

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confidence: 99%

Partitioning of water‐soluble vitamins in biodegradable aqueous two‐phase systems: Electrolyte perturbed‐chain statistical associating fluid theory predictions and experimental validation

et al. 2020

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“…Kinetics and yield of chemical and biochemical reactions strongly depend on the reaction solvent (Lemberg and Sadowski, 2017; Voges et al, 2017; Wangler et al, 2019). Figure 1 shows that this was also observed for the reaction under consideration in the present study.…”

Section: Resultsmentioning

confidence: 99%

Catalytic Low-Temperature Dehydration of Fructose to 5-Hydroxymethylfurfural Using Acidic Deep Eutectic Solvents and Polyoxometalate Catalysts

2019

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HMF synthesis typically requires high temperature and is carried out in aqueous solutions. In this work, the low-temperature dehydration of fructose to HMF in different deep eutectic solvents (DES) was investigated. We found a very active and selective reaction system consisting of the DES tetraethyl ammonium chloride as hydrogen bond acceptor (HBA) and levulinic acid as hydrogen bond donor (HBD) in a molar ratio of 1:2 leading to a maximum HMF yield of 68% after 120 h at 323 K. The DES still contained a low amount of water at the initial reaction, and water was also produced during the reaction. Considering the DES properties, neither the molar ratio in the DES nor the reaction temperature had a significant influence on the overall performance of the reaction system. However, the nature of the HBA as well as the acidity of the HBD play an important role for the maximum achievable HMF yield. This was validated by measured yields in a DES with different combinations of HBD (levulinic acid and lactic acid) and HBA (choline chloride and tetra-n-alkyl ammonium chlorides). Moreover, addition of vanadium containing catalysts, especially the polyoxometalate HPA-5 (H8PV5Mo7O40) leads to drastically increased reaction kinetics. Using HPA-5 and the DES tetraethyl ammonium chloride—levulinic acid we could reach a maximum HMF yield of 57% after only 5 h reaction time without decreasing the very high product selectivity.

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“…In this work, species-averaged activity coefficients of NAD + and NADH were used to reduce the complexity of the system without sacrificing the quality of the predictions as shown in previous works and thus K th reference to the biochemical reference state commonly indicated by K th ′ . 10,15,16 As K x obs (the ratio of the mole fractions of the reacting agents at equilibrium) strongly depends on kind and concentration of the cosolvent, it is further referred to as an observed (obs) value; thus, it is not a constant value. In contrast to eq 1, the activity of H + is transferred to the side of K th in eq 2.…”

Section: Theoretical Frameworkmentioning

confidence: 99%

“…Thus, (micro-)organisms use substrate concentrations often not much higher than the value for the Michaelis constant. 8,9 While the reaction equilibrium is known to be independent of the catalyst as long as the catalyst is present at low concentration, 10−14 the reaction rate and Michaelis constants strongly depend on the catalyst. 15,16 Further, both, reaction equilibrium and Michaelis constants strongly depend on the reaction medium, which might be tuned by the addition of cosolvents.…”

Section: Introductionmentioning

confidence: 99%

Simultaneous Prediction of Cosolvent Influence on Reaction Equilibrium and Michaelis Constants of Enzyme-Catalyzed Ketone Reductions

et al. 2019

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Understanding and quantification of cosolvent influences on enzyme-catalyzed reactions are driven by a twofold interest. On the one hand, cosolvents can simulate the cellular environment for deeper understanding of in cellulo reaction conditions. On the other hand, cosolvents are applied in biotechnology to tune yield and kinetics of reactions. Further, cosolvents are even present inherently, for example, for reactions with cofactor regeneration or for enzymes that need cosolvents in a function of a stabilizer. As the experimental determination of yield and kinetics is costly and time consuming, this work aims at providing a thermodynamic predictive approach that might allow screening cosolvent influences on yield and Michaelis constants. Reactions investigated in this work are the reduction of butanone and 2-pentanone under the influence of 17 wt % of the cosolvent polyethylene glycol 6000, which is also often used as a crowder to simulate cellular environments. The considered reactions were catalyzed by a genetically modified alcohol dehydrogenase (ADH 270). Predictions of cosolvent influences are based on accounting for a cosolvent-induced change of molecular interactions among the reacting agents as well as between the reacting agents and the solvent. Such interactions were characterized by activity coefficients of the reacting agents that were predicted by means of electrolyte perturbed-chain statistical associating fluid theory. This allowed simultaneously predicting the cosolvent effects on yield and Michaelis constants for two-substrate reactions for the first time.

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Predicting the high concentration co-solvent influence on the reaction equilibria of the ADH-catalyzed reduction of acetophenone

Cited by 20 publications

References 38 publications

Partitioning of water‐soluble vitamins in biodegradable aqueous two‐phase systems: Electrolyte perturbed‐chain statistical associating fluid theory predictions and experimental validation

Partitioning of water‐soluble vitamins in biodegradable aqueous two‐phase systems: Electrolyte perturbed‐chain statistical associating fluid theory predictions and experimental validation

Catalytic Low-Temperature Dehydration of Fructose to 5-Hydroxymethylfurfural Using Acidic Deep Eutectic Solvents and Polyoxometalate Catalysts

Simultaneous Prediction of Cosolvent Influence on Reaction Equilibrium and Michaelis Constants of Enzyme-Catalyzed Ketone Reductions

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