Keplerate {Mo132}–Stearic Acid Conjugates:
Supramolecular Synthons for the Design of Dye-Loaded Nanovesicles,
Langmuir–Schaefer Films, and Infochemical Applications
posted on 2024-02-01, 14:33authored byAndrey Denikaev, Yulia Kuznetsova, Alexey Bykov, Arkadiy Zhilyakov, Ksenia Belova, Pavel Abramov, Nikolai Moskalenko, Ekaterina Skorb, Kirill Grzhegorzhevskii
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 dyeseriochrome 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.