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Theoretical Insights into the Ultrafast Deactivation Mechanism and Photostability of a Natural Sunscreen System: Mycosporine Glycine.

ABSTRACT: In this work, different levels of quantum computational models such as MP2, ADC(2), CASSCF/CASPT2, and DFT/TD-DFT have been employed to investigate the photophysics and photostability of a mycosporine system, mycosporine glycine (MyG). First of all, a molecular mechanics approach based on the Monte Carlo conformational search has been employed to investigate the possible geometry structures of MyG. Then, comprehensive studies on the electronic excited states and deactivation mechanism have been conducted on the most stable conformer. The first optically bright electronic transition responsible for the UV absorption of MyG has been assigned as the S₂ (¹ππ*) owing to the large oscillator strength (0.450). The first excited electronic state (S₁) has been assigned as an optically dark (¹nπ*) state. From the nonadiabatic dynamics simulation model, we propose that the initial population in the S₂ (¹ππ*) state transfers to the S₁ state in under 100 fs, through an S₂/S₁ conical intersection (CI). The barrierless S₁ potential energy curves then drive the excited system to the S₁/S₀ CI. This latter CI provides a significant route for ultrafast deactivation of the system to the ground state via internal conversion.

SUBMITTER: Omidyan R

PROVIDER: S-EPMC10258844 | biostudies-literature | 2023 Jun

REPOSITORIES: biostudies-literature

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Theoretical Insights into the Ultrafast Deactivation Mechanism and Photostability of a Natural Sunscreen System: Mycosporine Glycine.

Omidyan Reza R Shahrokh Leila L Whittock Abigail L AL Stavros Vasilios G VG

The journal of physical chemistry. A 20230530 22

In this work, different levels of quantum computational models such as MP2, ADC(2), CASSCF/CASPT2, and DFT/TD-DFT have been employed to investigate the photophysics and photostability of a mycosporine system, mycosporine glycine (MyG). First of all, a molecular mechanics approach based on the Monte Carlo conformational search has been employed to investigate the possible geometry structures of MyG. Then, comprehensive studies on the electronic excited states and deactivation mechanism have been ...[more]

PMID: 37252729

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Project description:BackgroundMycosporine-like amino acids (MAAs), including shinorine and porphyra-334, are gaining attention as safe natural sunscreens. The production of MAAs has been achieved in diverse microbial hosts, including Saccharomyces cerevisiae. While S. cerevisiae is the most extensively studied model yeast, the oleaginous yeast Yarrowia lipolytica has emerged as a promising candidate for the synthesis of valuable products. In this study, we explored the potential of Y. lipolytica as a host for producing MAAs, utilizing its advantages such as a robust pentose phosphate pathway flux and versatile carbon source utilization.ResultsWe produced MAAs in Y. lipolytica by introducing the MAA biosynthetic genes from cyanobacteria Nostoc punctiforme and Anabaena variabilis. These genes include mysA, mysB, and mysC responsible for producing mycosporine-glycine (MG) from sedoheptulose 7-phosphate (S7P). The two strains utilize different enzymes, D-Ala-D-Ala ligase homologue (MysD) in N. punctiforme and NRPS-like enzyme (MysE) in A. variabilis, for amino acid conjugation to MG. MysE specifically generated shinorine, a serine conjugate of MG, while MysD exhibited substrate promiscuity, yielding both shinorine and a small amount of porphyra-334, a threonine conjugate of MG. We enhanced MAAs production by selecting mysA, mysB, and mysC from A. variabilis and mysD from N. punctiforme based on their activities. We further improved production by strengthening promoters, increasing gene copies, and introducing the xylose utilization pathway. Co-utilization of xylose with glucose or glycerol increased MAAs production by boosting the S7P pool through the pentose phosphate pathway. Overexpressing GND1 and ZWF1, key genes in the pentose phosphate pathway, further enhanced MAAs production. The highest achieved MAAs level was 249.0 mg/L (207.4 mg/L shinorine and 41.6 mg/L of porphyra-334) in YP medium containing 10 g/L glucose and 10 g/L xylose.ConclusionsY. lipolytica was successfully engineered to produce MAAs, primarily shinorine. This achievement involved the introduction of MAA biosynthetic genes from cyanobacteria, establishing xylose utilizing pathway, and overexpressing the pentose phosphate pathway genes. These results highlight the potential of Y. lipolytica as a promising yeast chassis strain for MAAs production, notably attributed to its proficient expression of MysE enzyme, which remains non-functional in S. cerevisiae, and versatile utilization of carbon sources like glycerol.

Dataset Information

Theoretical Insights into the Ultrafast Deactivation Mechanism and Photostability of a Natural Sunscreen System: Mycosporine Glycine.

Publications

Theoretical Insights into the Ultrafast Deactivation Mechanism and Photostability of a Natural Sunscreen System: Mycosporine Glycine.

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