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Theoretical Study of the Photoisomerization Mechanism of All-Trans-Retinyl Acetate.

ABSTRACT: The compound 9-cis-retinyl acetate (9-cis-RAc) is a precursor to 9-cis-retinal, which has potential application in the treatment of some hereditary diseases of the retina. An attractive synthetic route to 9-cis-RAc is based on the photoisomerization reaction of the readily available all-trans-RAc. In the present study, we examine the mechanism of the photoisomerization reaction with the use of state-of-the-art electronic structure calculations for two polyenic model compounds: tEtEt-octatetraene and tEtEtEc-2,6-dimethyl-1,3,5,7,9-decapentaene. The occurrence of photoisomerization is attributed to a chain-kinking mechanism, whereby a series of S₁/S₀ conical intersections associated with kinking deformations at different positions along the polyenic chain mediate internal conversion to the S₀ state, and subsequent isomerization around one of the double bonds. Two other possible photoisomerization mechanisms are taken into account, but they are rejected as incompatible with simulation results and/or the available spectroscopic data.

SUBMITTER: Kochman MA

PROVIDER: S-EPMC8488936 | biostudies-literature | 2021 Sep

REPOSITORIES: biostudies-literature

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Theoretical Study of the Photoisomerization Mechanism of All-Trans-Retinyl Acetate.

Kochman Michał Andrzej MA Palczewski Krzysztof K Kubas Adam A

The journal of physical chemistry. A 20210921 38

The compound 9-cis-retinyl acetate (9-cis-RAc) is a precursor to 9-cis-retinal, which has potential application in the treatment of some hereditary diseases of the retina. An attractive synthetic route to 9-cis-RAc is based on the photoisomerization reaction of the readily available all-trans-RAc. In the present study, we examine the mechanism of the photoisomerization reaction with the use of state-of-the-art electronic structure calculations for two polyenic ...[more]

PMID: 34546761

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Project description:Background: Increased cancer rates denote that one in two people will be diagnosed with cancer in their lifetime. Over 60% of cancer patients receive radiotherapy, either as a stand-alone treatment or in combination with other treatments such as chemotherapy and surgery. Whilst radiotherapy is effective in destroying cancer cells, it also causes subsequent damage to healthy cells and surrounding tissue due to alterations in the tumor microenvironment and an increase in reactive oxygen species (ROS). This can cause extensive damage that impairs tissue function, and the likelihood of tissue regeneration and restoration of function is significantly reduced as new healthy cells cannot survive in the damaged environment. In the treatment of head and neck cancers, radiotherapy can cause salivary gland dysfunction. This significantly impairs the patient's quality of life and there is currently no cure, only palliative treatment options. Tissue engineering approaches are used to mimic the microenvironment of the tissue and can mediate the damaged microenvironment via bioactive compounds, to support the delivery, survival, and proliferation of new, healthy cells into the damaged environment. Methods: In this study, retinyl acetate, a derivative of vitamin A, was successfully incorporated into electrospun polycaprolactone fibres. Results: SEM images and characterization analyses showed that all scaffolds produced had similar characteristics, including fiber morphology and scaffold wettability. The vitamin scaffolds were shown to exert an antioxidant effect through scavenging activity of both DPPH and hydroxyl radicals in vitro. Critically, the antioxidant scaffolds supported the growth of human submandibular gland cells and significantly upregulated the expression of GPx1, an antioxidant enzyme, when cultured under both normal conditions and under a simulated oxidative stress environment. Discussion: These results suggest that incorporation of retinyl acetate into electrospun fibres has may mediate the damaged microenvironment post cancer radiation therapy.

Dataset Information

Theoretical Study of the Photoisomerization Mechanism of All-Trans-Retinyl Acetate.

Publications

Theoretical Study of the Photoisomerization Mechanism of All-<i>Trans</i>-Retinyl Acetate.

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