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Effects of Clay Nanosheets on the Photostability of Cationic Porphyrin.

ABSTRACT: The photodecomposition behavior of cationic porphyrin ZnTMAP⁴⁺ (zinc tetrakis-(N,N,N-trimethylanilinium-4-yl) porphyrin) in water and complexed with clay nanosheets was investigated by light irradiation to the Soret band of ZnTMAP⁴⁺. The decomposition of ZnTMAP⁴⁺ was observed by UV-visible absorption spectroscopy. While the decomposition quantum yield (ϕ_dec) was 3.4 × 10^-4 in water, that was 9.4 × 10^-7 on the exfoliated clay nanosheets. It was revealed that the photostability of ZnTMAP⁴⁺ was stabilized by the complex formation with clay. When ZnTMAP⁴⁺ was intercalated between the stacked clay nanosheets, ϕ_dec was further decreased to 4.9 × 10^-7. The photostability increased by 361 times and 693 times for the exfoliated and stacked state, respectively. These results indicate that the flat clay surface has the potential to control intra- and intermolecular photochemical reactions.

SUBMITTER: Tahara Y

PROVIDER: S-EPMC11357654 | biostudies-literature | 2024 Aug

REPOSITORIES: biostudies-literature

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Effects of Clay Nanosheets on the Photostability of Cationic Porphyrin.

Tahara Yoshinori Y Hirade Yugo Y Arakawa Kyosuke K Shimada Tetsuya T Ishida Tamao T Tachibana Hiroshi H Takagi Shinsuke S

Molecules (Basel, Switzerland) 20240807 16

The photodecomposition behavior of cationic porphyrin ZnTMAP4+ (zinc tetrakis-(N,N,N-trimethylanilinium-4-yl) porphyrin) in water and complexed with clay nanosheets was investigated by light irradiation to the Soret band of ZnTMAP4+. The decomposition of ZnTMAP4+ was observed by UV-visible absorption spectroscopy. While the decomposition quantum yield (ϕdec) was 3.4 × 10-4 in water, that was 9.4 × 10-7 ...[more]

PMID: 39202818

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Project description:Colloidal clay nanosheets obtained by the delamination of layered crystals of smectite-type clay minerals in water form liquid crystals because of their shape anisotropy. Loading of organic dyes onto the liquid crystalline clay nanosheets will enable novel photonic materials, where photofunctions of the loaded dye are controlled by the liquid crystallinity of the clay nanosheets. However, adsorption of organic dyes onto the nanosheets renders the nanosheet surfaces hydrophobic, and consequently, colloidal stability of the nanosheets is lost. In this study, this drawback is overcome by sandwiching cationic stilbazolium dyes between a pair of synthetic fluorohectorite nanosheets. This is realized by the preparation of stilbazolium-clay second-stage intercalation compounds characterized by intercalation of dye cations into every other interlayer space of the hectorite clay, where nonintercalated interlayer spaces are occupied by Na+ ions. The second-stage intercalation compounds are obtained by partial ion exchange of mother clay mineral incorporating Na+ ions in all of the interlayer spaces and delaminated from the Na+-containing interlayer spaces to form clay nanosheets sandwiching the dye molecules. Aqueous colloids of the dye-sandwiching clay nanosheets form colloidal liquid crystals, and the dye-sandwiching liquid crystalline clay nanosheets respond to an applied AC electric field to be aligned parallel to the electric field. The assembled structure of the dye-sandwiching clay nanosheets under the electric field is characterized by aligned discrete clay platelets, which is somewhat different from that of a colloidal liquid crystal of clay nanosheets without dye loading characterized by macroscopic liquid crystalline domains up to submillimeters. The electric alignment of the clay nanosheets induces alteration of light absorption of the sandwiched stilbazolium molecules, which verifies a strategy of constructing stimuli-responsive photonic materials of clay-organic hybrids.

Dataset Information

Effects of Clay Nanosheets on the Photostability of Cationic Porphyrin.

Publications

Effects of Clay Nanosheets on the Photostability of Cationic Porphyrin.

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