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Large Amplitude Motions of Pyruvic Acid (CH3-CO-COOH).

ABSTRACT: Torsional and rotational spectroscopic properties of pyruvic acid are determined using highly correlated ab initio methods and combining two different theoretical approaches: Second order perturbation theory and a variational procedure in three-dimensions. Four equilibrium geometries of pyruvic acid, Tc, Tt, Ct, and CC, outcome from a search with CCSD(T)-F12. All of them can be classified in the Cs point group. The variational calculations are performed considering the three internal rotation modes responsible for the non-rigidity as independent coordinates. More than 50 torsional energy levels (including torsional subcomponents) are localized in the 406-986 cm-1 region and represent excitations of the ν24 (skeletal torsion) and the ν23 (methyl torsion) modes. The third independent variable, the OH torsion, interacts strongly with ν23. The A1/E splitting of the ground vibrational state has been evaluated to be 0.024 cm-1 as it was expected given the high of the methyl torsional barrier (338 cm-1). A very good agreement with respect to previous experimental data concerning fundamental frequencies (νCAL - νEXP ~ 1 cm-1), and rotational parameters (B0CAL - B0EXP < 5 MHz), is obtained.

SUBMITTER: Senent ML

PROVIDER: S-EPMC8303138 | biostudies-literature | 2021 Jul

REPOSITORIES: biostudies-literature

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Large Amplitude Motions of Pyruvic Acid (CH<sub>3</sub>-CO-COOH).

Senent María Luisa ML Dalbouha Samira S

Molecules (Basel, Switzerland) 20210714 14

Torsional and rotational spectroscopic properties of pyruvic acid are determined using highly correlated ab initio methods and combining two different theoretical approaches: Second order perturbation theory and a variational procedure in three-dimensions. Four equilibrium geometries of pyruvic acid, Tc, Tt, Ct, and CC, outcome from a search with CCSD(T)-F12. All of them can be classified in the C<sub>s</sub> point group. The variational calculations are performed considering the three internal ...[more]

PMID: 34299546

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Project description:The structure of zymonic acid (systematic name: 4-hy-droxy-2-methyl-5-oxo-2,5-di-hydro-furan-2-carb-oxy-lic acid), C6H6O5, which had previously eluded crystallographic determination, is presented here for the first time. It forms by intra-molecular condensation of parapyruvic acid, which is the product of aldol condensation of pyruvic acid. A redetermination of the crystal structure of pyruvic acid (systematic name: 2-oxo-propanoic acid), C3H4O3, at low temperature (90 K) and with increased precision, is also presented [for the previous structure, see: Harata et al. (1977 ▸). Acta Cryst. B33, 210-212]. In zymonic acid, the hy-droxy-lactone ring is close to planar (r.m.s. deviation = 0.0108 Å) and the dihedral angle between the ring and the plane formed by the bonds of the methyl and carb-oxy-lic acid carbon atoms to the ring is 88.68 (7)°. The torsion angle of the carb-oxy-lic acid group relative to the ring is 12.04 (16)°. The pyruvic acid mol-ecule is almost planar, having a dihedral angle between the carb-oxy-lic acid and methyl-ketone groups of 3.95 (6)°. Inter-molecular inter-actions in both crystal structures are dominated by hydrogen bonding. The common R 2 2(8) hydrogen-bonding motif links carb-oxy-lic acid groups on adjacent mol-ecules in both structures. In zymonic acid, this results in dimers about a crystallographic twofold of space group C2/c, which forces the carb-oxy-lic acid group to be disordered exactly 50:50, which scrambles the carbonyl and hydroxyl groups and gives an apparent equalization of the C-O bond lengths [1.2568 (16) and 1.2602 (16) Å]. The other hydrogen bonds in zymonic acid (O-H⋯O and weak C-H⋯O), link mol-ecules across a 21-screw axis, and generate an R 2 2(9) motif. These hydrogen-bonding inter-actions propagate to form extended pleated sheets in the ab plane. Stacking of these zigzag sheets along c involves only van der Waals contacts. In pyruvic acid, inversion-related mol-ecules are linked into R 2 2(8) dimers, with van der Waals inter-actions between dimers as the only other inter-molecular contacts.

Project description:BackgroundIndole pyruvic acid (IPA) is a versatile platform intermediate and building block for a number of high-value products in the pharmaceutical and food industries. It also has a wide range of applications, such as drugs for the nervous system, cosmetics, and luminophores. Chemical synthesis of IPA is a complicated and costly process. Moreover, through the biosynthesis route employing L-amino acid oxidase, the byproduct hydrogen peroxide leads the degradation of IPA. TdiD, identified as a specific tryptophan aminotransferase, could be an alternative solution for efficient IPA biosynthesis.ResultsEscherichia coli strain W3110, which demonstrates basic production when supplied with tryptophan, was engineered for IPA biosynthesis. Several strategies were implemented to improve IPA production. First, through incorporating the codon-optimized tdiD into W3110, IPA levels increased from 41.54 ± 1.26 to 52.54 ± 2.08 mg/L. Second, after verifying the benefit of an increased phenylpyruvate pool, a YL03 strain was constructed based on a previously reported mutant strain of W3110 with a plasmid carrying aroF fbr and pheA fbr to further improve IPA production. The recombinant YL03 strain accumulated IPA at 158.85 ± 5.36 mg/L, which was 3.82-fold higher than that of the wild-type W3110 strain. Third, optimization of tdiD co expression was carried out by replacing the Trc promoter with a series of constitutively active promoters along with increasing the plasmid copy numbers. The highest IPA production was observed in YL08, which achieved 236.42 ± 17.66 mg/L and represented a greater than 5-fold increase as compared to W3110. Finally, the effects of deletion and overexpression of tnaA on IPA biosynthesis were evaluated. The removal of tnaA led to slightly reduced IPA levels, whereas the overexpression of tnaA resulted in a considerable decline in production.ConclusionsThis study illustrates the feasibility of IPA biosynthesis in E. coli through tdiD. An efficient IPA producing strain, YL08, was developed, which provides a new possibility for biosynthesis of IPA. Although the final production was limited, this study demonstrates a convenient method of IPA synthesis.

Dataset Information

Large Amplitude Motions of Pyruvic Acid (CH3-CO-COOH).

Publications

Large Amplitude Motions of Pyruvic Acid (CH<sub>3</sub>-CO-COOH).

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