Nanocluster Polyoxometalates Functional Design
Grzhegorzhevskii LAB
LAB SCOPE
Polyoxometalate (POM) chemistry spans across the coordination compounds and the hierarchical supramolecular ensembles. Only five elements (V, Mo, W, Nb and Ta) possess the unique combination of ionic radius and atom shell configuration to produce diversity in polynuclear iso- and hetero-complexes: Evans–Anderson, Keggin, Well–Dawson and even giant POM-like Keplerates, etc.
POM exhibit various scenarios when being embedded into hybrid organic structures via coordination and electrostatic interactions, weak van der Waals forces and hydrogen bonding. Along with the possibility to graft the organic linkers, the POMs are a powerful platform for the design of supramolecular architectures.
Using POM as a nano-scaled template, we create supramolecular structures for photocatalysis, biomimetics and molecular recognition applications.
Research Topics
Interaction POM-Sensitizer
The giant POM (like Keplerate-type etc.) can either induce organic dye self-assembling on its surface or participate in dynamic supramolecular ensembles formation. Using different cationic dyes (xanthene dyes, porphyrins, BODIPY etc.) we can flexibly tune the electron and energy transfer process on the POM surface to control the photocatalytic behaviour. Furthermore, POM|Dye is prominent system to answer on two essential questions:
i) how dye aggregation affects the photoeficiency on metal-oxide|dye interfaces in solar cell;
ii) how we can control the aggregation.
The giant POM (like Keplerate-type etc.) can either induce organic dye self-assembling on its surface or participate in dynamic supramolecular ensembles formation. Using different cationic dyes (xanthene dyes, porphyrins, BODIPY etc.) we can flexibly tune the electron and energy transfer process on the POM surface to control the photocatalytic behaviour. Furthermore, POM|Dye is prominent system to answer on two essential questions:
i) how dye aggregation affects the photoeficiency on metal-oxide|dye interfaces in solar cell;
ii) how we can control the aggregation.
Giant POM Covalent Modification
Using alkoxysilanes our Lab performed pioneer research on covalently grafting of the organic molecules onto the giant POM surface and realized postfunctionalization by means of click-reaction (carbodiimide, thiol-ene, Schiff-base etc.). As a result, giant POMs surve like precise (2.5 or 3 nm diameter) nanoscaled inorganic templates to assemble desired supramolecular structures for many kind of applications: photo- and regioselective catalysis, nano-vesicles formation, Langmuir-Blodgett films etc. Our strategy suggests powerful instrument to tune the smart-materials on the supramolecular level using giant POMs.
Using alkoxysilanes our Lab performed pioneer research on covalently grafting of the organic molecules onto the giant POM surface and realized postfunctionalization by means of click-reaction (carbodiimide, thiol-ene, Schiff-base etc.). As a result, giant POMs surve like precise (2.5 or 3 nm diameter) nanoscaled inorganic templates to assemble desired supramolecular structures for many kind of applications: photo- and regioselective catalysis, nano-vesicles formation, Langmuir-Blodgett films etc. Our strategy suggests powerful instrument to tune the smart-materials on the supramolecular level using giant POMs.
Hybrid Hydrogel and Drug Carriers
Due to the polyfunctional surface the giant POM can be embedded into hydrogel structure via electrostatic or Wan-der-Waals forces, hydrogen bonding and covalent grafting. As a template, POM macroanion can organize macromolecules in specific fashion (like electrostatic linker for catinic polyelectrolyte e.g.). As a result, we can control the swelling behaviour of hydrogel or loaded them with desired drug bound with POM surface. During the pH-depended POM destruction, the stored drug can be released in controled fashion. Furthermore, once covalently modify the polymer chain by organic dye, we can create multifunctional POM-embedded biocomatible hydrogel for bioapplication.
Due to the polyfunctional surface the giant POM can be embedded into hydrogel structure via electrostatic or Wan-der-Waals forces, hydrogen bonding and covalent grafting. As a template, POM macroanion can organize macromolecules in specific fashion (like electrostatic linker for catinic polyelectrolyte e.g.). As a result, we can control the swelling behaviour of hydrogel or loaded them with desired drug bound with POM surface. During the pH-depended POM destruction, the stored drug can be released in controled fashion. Furthermore, once covalently modify the polymer chain by organic dye, we can create multifunctional POM-embedded biocomatible hydrogel for bioapplication.
Machine Learning for Supramolecular Structure Design
We combine Machine Learning and cyclic voltammetry to find the way to produce supramolecular structures in controlled fashion based on the giant POM (like Keplerate) and cationic organic dyes. The global aim is software product which can predict supramolecular behaviour in such systems based on the electrochemical data. Using robot-assisted screening experiments we believe that machine learning can solve this challenge through artificial intellegence approach.
We combine Machine Learning and cyclic voltammetry to find the way to produce supramolecular structures in controlled fashion based on the giant POM (like Keplerate) and cationic organic dyes. The global aim is software product which can predict supramolecular behaviour in such systems based on the electrochemical data. Using robot-assisted screening experiments we believe that machine learning can solve this challenge through artificial intellegence approach.
PUBLICATIONS
Recent Results
Molecular Recognition on the Multisite Binding Surface of the Keplerate {Mo72Fe30} Giving Supramolecular Texturing and Modulating the Function of Guest Molecules
Inorganic Chemistry, 63(38), 17 388−17 405
https://doi.org/10.1021/acs.inorgchem.4c01338
Inorganic Chemistry, 63(38), 17 388−17 405
https://doi.org/10.1021/acs.inorgchem.4c01338
Covalent Grafting of Eosin Y to the Giant Keplerate {Mo132} through an Organosilicon Linker in Homogeneous Regime
Inorganics, 11(6), 239.
https://doi.org/10.3390/inorganics11060239
Inorganics, 11(6), 239.
https://doi.org/10.3390/inorganics11060239
Polyacrylamide-chitosan semi-interpenetrating self-healing network with embedded Keplerate {Mo132 } for pH-controlled release of Eu-fluorescent tags
New Journal of Chemistry, 47, 17 007−17 019
https://doi.org/10.1039/D3NJ03041E
New Journal of Chemistry, 47, 17 007−17 019
https://doi.org/10.1039/D3NJ03041E
Keplerate {Mo132}–Stearic Acid Conjugates: Supramolecular Synthons for the Design of Dye-Loaded Nanovesicles, Langmuir–Schaefer Films, and Infochemical Applications
ACS Applied Materials & Interfaces (2024)
https://doi.org/10.1021/acsami.3c16374
ACS Applied Materials & Interfaces (2024)
https://doi.org/10.1021/acsami.3c16374
Fundamental Aspects of Xanthene Dye Aggregation on the Surfaces of Nanocluster Polyoxometalates: H‐ to J‐Aggregate Switching
Chemistry – A European Journal, 26(25), 5685-5693.
https://doi.org/10.1002/chem.201905781
Chemistry – A European Journal, 26(25), 5685-5693.
https://doi.org/10.1002/chem.201905781
The precise modification of a nanoscaled Keplerate-type polyoxometalate with NH2-groups: reactive sites, mechanisms and dye conjugation
Inorganic Chemistry Frontiers, 9(7), 1541-1555.
https://doi.org/10.1039/d1qi01454d
Inorganic Chemistry Frontiers, 9(7), 1541-1555.
https://doi.org/10.1039/d1qi01454d
Gigantic supramolecular assemblies built from dynamic hierarchical organization between inorganic nanospheres and porphyrins
Chemical Communications 59, 86-89.
https://doi.org/10.1039/D2CC05193A
Chemical Communications 59, 86-89.
https://doi.org/10.1039/D2CC05193A
COLLABORATION AND FUNDING
Funding
#23-73-10158, "Multilayer photopolymerized inorganic-organic hydrogel system with fluorescent response and controlled drug release of quorum sensing inhibitors for wound dressing and regeneration" funded by Russian Science Foundation, 2023-2026.
#4.81, “Laboratory of the Nanocluster Polyoxometalates Functional Design” in frame of program “Priority 2030” of the Ministry of Science and Higher Education of the Russia Federation, 2022-2024.
#21-73-00311, “Design's strategies of nanoscaled polyoxometalates by molecules of oligopyrrole dyes: precise aggregation control of photosensitizers and creation of molecular scaffolds for photocatalytic applications” funded by Russian Science Foundation, 2021-2023.
#19-73-00177, "Durable action releasing-systems for drug delivery with feedback function based on the nanocluster polyoxometalates" funded by Russian Science Foundation, 2019-2021.
#SP-1070.2018.4 “Hybrid inorganic-organic sensory covers for biodiagnostic chips” funded by the Council for Grants of the President of the Russian Federation, 2018-2020.
#16-33-00570 “Photosensitization processes and catalytic properties of the supramolecular system based on the toroidal nanoclustered polyoxomolybdate Mo138” funded by Russian Foundation for Basic Research, 2016-2017.
#23-73-10158, "Multilayer photopolymerized inorganic-organic hydrogel system with fluorescent response and controlled drug release of quorum sensing inhibitors for wound dressing and regeneration" funded by Russian Science Foundation, 2023-2026.
#4.81, “Laboratory of the Nanocluster Polyoxometalates Functional Design” in frame of program “Priority 2030” of the Ministry of Science and Higher Education of the Russia Federation, 2022-2024.
#21-73-00311, “Design's strategies of nanoscaled polyoxometalates by molecules of oligopyrrole dyes: precise aggregation control of photosensitizers and creation of molecular scaffolds for photocatalytic applications” funded by Russian Science Foundation, 2021-2023.
#19-73-00177, "Durable action releasing-systems for drug delivery with feedback function based on the nanocluster polyoxometalates" funded by Russian Science Foundation, 2019-2021.
#SP-1070.2018.4 “Hybrid inorganic-organic sensory covers for biodiagnostic chips” funded by the Council for Grants of the President of the Russian Federation, 2018-2020.
#16-33-00570 “Photosensitization processes and catalytic properties of the supramolecular system based on the toroidal nanoclustered polyoxomolybdate Mo138” funded by Russian Foundation for Basic Research, 2016-2017.
Thanks for support
contact us
Ural Federal University
Istitute of Natural Sciences and Mathematics
Institute of Applied Physics and Mathematic
Laboratory of Nanocluster Polyoxometalates
Functional Design
kirillvalentinovich@urfu.ru
Russia, Ekaterinburg, Kuybisheva street 48
*photo by Slava Kaygorodov and Anna Prokofyeva
Istitute of Natural Sciences and Mathematics
Institute of Applied Physics and Mathematic
Laboratory of Nanocluster Polyoxometalates
Functional Design
kirillvalentinovich@urfu.ru
Russia, Ekaterinburg, Kuybisheva street 48
*photo by Slava Kaygorodov and Anna Prokofyeva