Crystal-to-crystal photo-reversible polymerization mechanism of bis-thymine derivative

Udagawa, Akihiro; Johnston, Priscilla; Sakon, Aya; Toyoshima, Ryosuke; Uekusa, Hidehiro; Koshima, Hideko; Saito, Kei; Asahi, Toru

doi:10.1039/c6ra24229d

Cited by 5 publications

(9 citation statements)

References 38 publications

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“…We previously designed a bis-thymine monomer, n -butyl-linked-bis(thymine propanoate), which can undergo one-photon-induced [2 + 2] cycloaddition and cycloreversion upon irradiation with UV light in the solid crystalline state. − Here, we demonstrate that the same reaction could be achieved upon TP absorption (Figure ).…”

Section: Introductionmentioning

confidence: 56%

“…Such alteration is, in turn, caused by the strain imparted on the crystal lattice upon reorientation of the molecules, as reported by previous studies. 20 To investigate which product resulted from the irradiation, we initially conducted NMR measurements, which unfortunately resulted in no signal due to the low amount of sample. Consequently, we used Raman spectroscopy, as its sensitivity allows to analyze reactants at sub-micrometer scale.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…We hypothesize that such orientation dependence arises from the anisotropic nature of the crystals, in which molecules are packed unidirectionally. 20,26 Next, we aimed at evaluating the confinement volume of the reaction, and Raman mapping represents an excellent approach to asses it. Hence, a designated area in the sample (Figure 2a, red rectangle) was scanned with a laser and Raman spectra were collected point-by-point.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…As depicted in Figure a, changes in the crystal occurred after irradiation (round spots) and are provoked either by a modification in the material refractive index or by a crack generated in the crystal. Such alteration is, in turn, caused by the strain imparted on the crystal lattice upon reorientation of the molecules, as reported by previous studies …”

Section: Results and Discussionmentioning

confidence: 99%

“…Notably, we discovered that the cycloaddition yield strongly depends on the crystal orientation with respect to the light polarization (Figure S4). We hypothesize that such orientation dependence arises from the anisotropic nature of the crystals, in which molecules are packed unidirectionally. , …”

Section: Results and Discussionmentioning

confidence: 99%

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Two-Photon-Induced [2 + 2] Cycloaddition of Bis-thymines: A Biocompatible and Reversible Approach

et al. 2020

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Despite having great value across a wide variety of scientific fields, two-photon polymerizations currently suffer from two significant problems: the need for photoinitiators, which generate toxic side products, and the irreversibility of the process. Hence, the design of a versatile approach that circumvents these issues represents a major scientific challenge. Herein, we report a two-photon absorption strategy where reversible [2 + 2] cycloaddition of bis-thymines was achieved without the need for any photoinitiator. The cycloaddition and cycloreversion reactions could be induced by simply changing the irradiation wavelength, and repeated writing and erasing cycles were performed. The simplicity, reversibility, and biocompatibility of this strategy open up a whole new toolbox for applications across a wide variety of scientific fields.

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Section: Introductionmentioning

confidence: 56%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Results and Discussionmentioning

confidence: 99%

Section: Results and Discussionmentioning

confidence: 99%

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Two-Photon-Induced [2 + 2] Cycloaddition of Bis-thymines: A Biocompatible and Reversible Approach

et al. 2020

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Photo-conversion of self-assembled structures into continuous covalent structures via [2 + 2]-cycloaddition reactions

Inada

Udagawa

Sato

et al. 2022

Photochem Photobiol Sci

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In this study, the conversion of self-assembled structures into continuous polymeric structures by linking the self-assembled molecules using the [2 + 2]-cycloaddition reaction was investigated. Synthesized bio-inspired thymine-based bolaamphiphilic molecules were designed to force the interactions between two molecules to engage two thymines in their self-assembled structure to undergo a cycloaddition reaction. Thymine-based bolaamphiphilic molecules were designed and synthesized using different phenylene spacers based on aromatic substituents (ortho-) (meta-) (para-). The formed self-assembled structures from these molecules were characterized and compared using molecular mechanical simulations. Simulations were performed to discuss the relationship between the inter-and intramolecular cycloaddition sensitivity to different substituents. This study provides a strategy for creating higher molecular weight linear polymers by controlling the photocyclization sites within the self-assembly by spacers between thymines.

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Photoinduced Single-Crystal to Single-Crystal Transformation via Conformational Change with Turn-On Fluorescence

Liang

Tian

Yong

et al. 2022

Crystal Growth & Design

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Single-crystal to single-crystal (SCSC) transformation by phototrigger is presently attracting immense research interest in many fields such as sensors, actuators, artificial muscles, soft robotics, and energy harvesting. However, the only success of rare examples has been achieved by SCSC transformation so far, involving a change in molecular composition based on photocyclization reactions. Here, we show photoinduced SCSC transformation of 3-methylene-2-(quinolin-8-yl) isoindolin-1-one (MQIO) derivatives from monoclinic to triclinic phase via conformational change, just as "small input and big output". UV light induces a molecular conformation change of MQIO-H with rotation (11.3°) of the carbon−nitrogen single bond. The conformational changes of MQIO-H lead to the slides of molecular packing in crystals, finally resulting in the SCSC transformation from the monoclinic to the triclinic phase. In addition, the SCSC transformation was accompanied by turn-on fluorescence and shape changes of single crystal. The shape changes of single crystals can be clearly observed by UV light triggering under an optical microscope. This work provides a strategy to achieve SCSC transformation via photoinduction.

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Crystal-to-crystal photo-reversible polymerization mechanism of bis-thymine derivative

Abstract: Solid-state photo-reversible polymerization mechanism in crystals was studied, which can produce stereoregular polymer molecules in environmentally friendly solvent-free systems.

Cited by 5 publications

References 38 publications

Two-Photon-Induced [2 + 2] Cycloaddition of Bis-thymines: A Biocompatible and Reversible Approach

Two-Photon-Induced [2 + 2] Cycloaddition of Bis-thymines: A Biocompatible and Reversible Approach

Photo-conversion of self-assembled structures into continuous covalent structures via [2 + 2]-cycloaddition reactions

Photoinduced Single-Crystal to Single-Crystal Transformation via Conformational Change with Turn-On Fluorescence

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