Projects and grants

Porous polymer networks with helically chiral polyacetylene chains for enantioselective applications

The Chiral Porous Polymer Networks, CPPNs, representing chiral micro/mesoporous materials with newly designed combined character of chirality, will be developed. The CPPNs will combine (i) the chirality of covalently bonded groups containing asymmetric carbon atoms and (ii) the helical chirality of the main chain segments originating from their one-handed helical conformation stabilized by main chain cross-linking. The combined chirality of the CPPNs is very promising for their high efficiency in enantioselective applications that will be verified by evaluating CPPNs potential (i) in reversible enantioselective sorption of chiral drugs and fragrances and (ii) as enantioselective heterogeneous catalysts for hydrogenation, epoxidation and condensation reactions. Highly variable chain-growth polymerization of chiral and achiral ethynylarenes into polyacetylene-type hyper-cross-linked CPPNs is proposed as the main synthetic tool that will provide CPPNs with tuneable architecture, chirality and texture comprising various functional groups.

Principal investigator: doc. RNDr. Jan Sedláček, Dr.

Grantor: Czech Science Foundation 

Duration: 2021 to 2023 (prolonged to 06/2024)

Grant number: 21-02183S

Development of hydrophilic porous organic polymers for reversible adsorption of water vapor

Synthetic procedures will be developed and optimized that will be appropriate for the preparation of well covalently and texturally defined hydrophilic porous organic polymers, POPs (i.e. non-swelling polymers with permanent porosity and high specific surface area) potentially suitable for reversible adsorptive capture of water vapor from the gas phase. Four series of these POPs will be prepared differing primarily in the type of hydrophilic groups. With regard to the proposed application, POPs functionalized with the following groups will be developed and prepared: -COOH, -CH=O, -OH and -SO3H. Catalyzed chain-growth homo- and copolymerizations of ethynylated (co)monomers will be used to prepare proposed POPs. A hyper-cross-linked architecture of POPs will be achieved due to a higher average number of polymerizable ethynyl groups per (co)monomer molecule. Dense cross-linking by aromatic linkers together with the rigid nature of the main polyacetylene chains will ensure the primary porosity of POPs. Hydrophilic functional groups will be introduced into POPs by pre-polymerization functionalization (-COOH, -CH=O, -OH groups) or post-polymerization functionalization (-SO3H group). Prepolymerization functionalization will in some cases be combined with protecting group chemistry procedures. From the point of view of the covalent structure, the prepared POPs will differ in the content of the functional groups of the given type, in many cases the location of these functional groups and their mutual position in the networks will also be controlled.

Principal investigator: Ing. Michaela Vaňková

Grantor: Charles University Grant Agency 

Duration: 2023 to 2025

Grant number: 193223

Recently finished

Rational design of advanced soft functional materials guided by advanced solid-state NMR spectroscopy and high-performance electron microscopy

Materials based on pi-conjugated and coordinating polymers or metal-organic grids have considerable application potential due to their structural variability and their ability to store molecules and ions in their cavities. The overall goal of the project is the breakthrough in the design and development of application-interesting nanostructured amorphous materials, and optimization of their structure and functional properties with help of advanced solid state NMR methods, high resolution electron microscopy and computer simulations. New pieces of information, that are not available by conventional methods, should broaden our knowledge on their behavior and open new gate for rational design and reproducible preparation of novel soft matter systems for targeted applications. Several promising systems (structurally different) have been selected for testing the proposed strategy of tailored material research. Their structure, static and dynamic properties will be studied first and information gained will be used for their modification and for synthesis of better performing materials.

Principal investigator: Ing. Jiří Brus, Dr., Prof. RNDr. Karel Procházka, DrSc., doc. RNDr. Jan Sedláček, Dr.

Grantor: Czech Science Foundation 

Duration: 2020 to 2022 (prolonged to 06/2023)

Grant number: 20-01233S

Chiral Helical Polymers with Hyper-Cross-Linked Architecture for Enantioselective Applications

A new type of chiral porous polymer materials will be developed. The chiral character of the materials will be provided by the one-handed helical conformation of the polymer chains sometimes accompanied by chiral localized asymmetric carbon atoms in the pendant groups or cross-linkers (helical chiral polymers, HCP). The HCPs will be based on hyper-cross-linked substituted polyacetylenes with a wide spectrum of heteroatom functional groups. Cross-linking will stabilize the helical conformation of the chains and at the same time will support the formation of a permanent porous texture of HCPs. The research on the porosity of HCPs, especially with regard to hierarchical porosity, will be carried out in cooperation with the Institute of Chemistry in Ljubljana. The application potential of these materials will be focused on the actual tasks of chiral chemistry research. The HCPs will be tested as (i) reusable enantioselective heterogeneous catalysts of epoxidation and condensation reactions and (ii) sorbents for the enantioselective separation of chiral drugs and fragrances through reversible physi- and chemisorption.

Principal investigator: Mgr. David Šorm

Grantor: START 

Duration: 2021 to 2023

Grant number: START/SCI/081

Development of microporous hyper-cross-linked polymers with catalytically and sorption active segments of the quaternary ammonium salt type

The preparation of microporous organic polymers, MOPs (i.e., non-swelling polymers with permanent microporosity and high specific surface area), which will newly contain covalently inbuilt potentially functionally active quaternary ammonium salt-type groups, will be introduced and optimized, and several series of these materials will be prepared. The prepared MOPs will have the architecture of hyper-cross-linked polyacetylenes with different types of cross-linking and will further differ in the nature of the quaternary ammonium groups, their content and location either in the knots or the side groups of the network. Both catalyzed and non-catalyzed chain-growth homo- and copolymerization of predominantly multiethynylated monomers will be used which will be combined with a quaternization proceeding either in parallel with the polymerization or as a postpolymerization reaction. As key (co)monomers, compounds will be applied containing in addition to polymerizable ethynyl groups also precursors of quaternary ammonium salts, either in the form of tertiary amine or alkyl bromide type groups.
The prepared MOPs will be tested in two independent applications: (i) as heterogeneous catalysts for the reaction of substituted oxiranes with carbon dioxide and (ii) as sorbents for adsorption capture of water and lower alcohols from the gas phase. The functional potential of newly developed MOPs depending on their composition, structure and texture will be evaluated.

Principal investigator: Mgr. Alena Hašková

Grantor: Charles University Grant Agency 

Duration: 2020 to 2022

Grant number: 1296120

New microporous materials for sorption and catalytic applications based on functionalized hyper-cross-linked polyacetylenes

The method of preparation will be introduced and optimized that will allow preparing Microporous Organic Polymers, MOPs, (i.e. non-swelling polymers with permanent microporosity and high surface area) newly containing a high amount of oxygen (namely -CHO, -COOH, -CH2OH, -COONa), nitrogen (namely -CH2NH2, -CH=NRNHCH3) or organometallic groups (one or more groups per a building unit). As highly functionalized MOPs cannot be achieved via standard step-growth polymerizations, the method of chain polymerization will be optimized in the frame of the project that will provide MOPs in the form of polyacetylene networks. Functionalized MOPs will be achieved by: (i) homopolymerization of 1,3-diethynylbenzenes bearing a non-polymerizing functional group in position 5 and copolymerization of tetrakis(4-ethynyphenyl)methane with phenylacetylenes bearing two functional groups and (ii) homopolymerization of organometallic complexes bearing ethynyl groups on Schiff-base-type ligands. Some parent functionalized MOPs will be further modified via hydrolytic and condensation reactions. The prepared MOPs will be characterized in terms of the covalent structure, texture and morphology. The selected MOPs will be further studied with respect to their activity as heterogeneous catalysts of organic reactions and as sorbents in physi- and chemisorption and the functional potential of these materials will be assessed, depending on their composition and texture parameters.

Principal investigator: Mgr. Lucie Havelková

Grantor: Charles University Grant Agency 

Duration: 2019 to 2021

Grant number: 210119