TY - JOUR

T1 - Keplerate {Mo132}-Stearic Acid Conjugates: Supramolecular Synthons for the Design of Dye-Loaded Nanovesicles, Langmuir-Schaefer Films, and Infochemical Applications

AU - Denikaev, Andrey

AU - Kuznetsova, Yulia

AU - Bykov, Alexey

AU - Zhilyakov, Arkadiy

AU - Belova, Ksenia

AU - Abramov, Pavel

AU - Moskalenko, Nikolai

AU - Skorb, Ekaterina

AU - Grzhegorzhevskii, Kirill

N1 - The authors would like to acknowledge the Ministry of Science and Higher Education RF (project no. FEUZ-2023-0016) and Russian Science Foundation (project no. 23-73-10158 for support of the works concerning the POM-embedded gel study). The equipment of the Ural Center for Shared Use “Modern nanotechnology” Ural Federal University (Reg. no. 2968), which is supported by the Ministry of Science and Higher Education RF (project no. 075-15-2021-677), was used.

PY - 2024/2/14

Y1 - 2024/2/14

N2 - Self-assembly gives rise to the versatile strategies of smart material design but requires precise control on the supramolecular level. Here, inorganic-organic synthons (conjugates) are produced by covalently grafting stearic acid tails to giant polyoxometalate (POM) Keplerate-type {Mo132} through an organosilicon linker (3-aminopropyltrimethoxysilane, APTMS). Using the liposome production approach, the synthons self-assemble to form hollow nanosized vesicles (100-200 nm in diameter), which can be loaded with organic dyes─eriochrome black T (ErChB) and fluorescein (FL)─where the POM layer serves as a membrane with subnanopores for cell-like communication. The dye structure plays an essential role in embedding dyes into the vesicle’s shell, which opens the way to control the colloidal stability of the system. The produced vesicles are moved by an electric field and used for the creation of an infochemistry scheme with three types of logic gates (AND, OR, and IMP). To design 2D materials, synthons can form spread films, from simple addition on the water-air interface to lateral compression in the Langmuir bath, and highly ordered structures appear, demonstrating electron diffraction in Langmuir-Schaefer (LS) films. These results show the significant potential of POM-based synthons and nanosized vesicles to supramolecular design the diversity of smart materials.

AB - Self-assembly gives rise to the versatile strategies of smart material design but requires precise control on the supramolecular level. Here, inorganic-organic synthons (conjugates) are produced by covalently grafting stearic acid tails to giant polyoxometalate (POM) Keplerate-type {Mo132} through an organosilicon linker (3-aminopropyltrimethoxysilane, APTMS). Using the liposome production approach, the synthons self-assemble to form hollow nanosized vesicles (100-200 nm in diameter), which can be loaded with organic dyes─eriochrome black T (ErChB) and fluorescein (FL)─where the POM layer serves as a membrane with subnanopores for cell-like communication. The dye structure plays an essential role in embedding dyes into the vesicle’s shell, which opens the way to control the colloidal stability of the system. The produced vesicles are moved by an electric field and used for the creation of an infochemistry scheme with three types of logic gates (AND, OR, and IMP). To design 2D materials, synthons can form spread films, from simple addition on the water-air interface to lateral compression in the Langmuir bath, and highly ordered structures appear, demonstrating electron diffraction in Langmuir-Schaefer (LS) films. These results show the significant potential of POM-based synthons and nanosized vesicles to supramolecular design the diversity of smart materials.

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U2 - 10.1021/acsami.3c16374

DO - 10.1021/acsami.3c16374

M3 - Article

VL - 16

SP - 7430

EP - 7443

JO - ACS applied materials & interfaces

JF - ACS applied materials & interfaces

SN - 1944-8244

IS - 6

ER -