Podstrona: Projects / Prof. Paweł Chmielarz, Eng, PhD, DSc, ProfTit

Projects

Projects

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Project Number: UMO-2016/22/E/NZ7/00641

Project implemented under the SONATA BIS 6 program

Project title: Nanoparticle antioxidants: biological foundations for potential targeted therapy of neurodegenerative diseases.

Project Promoter: University of Rzeszów

Principal Investigator: Prof. Izabela Anna Sadowska-Bartosz, PhD, DSc, ProfTit

Project Value: 1 668 800,00 PLN

Time of realization: 27.03.2017 – 30.09.2022 (PRz involvement: 21.03.2022 – 30.09.2022)

Project financed by Polish National Science Centre (NCN)

Aim of the Project:

The aim of the project is: (i) synthesis of nano-antioxidants containing nitroxyl free radicals, (ii) analysis of their penetration into cells, (iii) assessment of their toxicity to cells (iv) effectiveness in alleviating oxidative (OS)/nitrative (NS) stress and its effects. The main goal of the project is to test the cytotoxicity and efficacy of two selected covalently bonded nitroxides (NZN) in ameliorating the pathological effects of alterations in animal models of Alzheimer's disease (AD) and Parkinson's disease (PD). The project also aims to analyze in detail the mechanism of involvement of NZN in anti-degenerative protection of nerve cells.

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Project Number: SKN/SP/534777/2022

Project implemented as part of the "Student science clubs create innovation" financed by the Ministry of Science and Education

Title of the project: Synthesis of conductive polymer materials inspired by the principles of green chemistry

Principal Investigator: Prof. Paweł Chmielarz, Eng, PhD, DSc, ProfTit

Project Value: 69 861,00 PLN

Financing with resources of Ministry of Education and Science, Poland

Aim of the Project:

The main object of the project is a synthesis of innovative and conductive polymer materials by applying methods of atom transfer radical polymerization (ATRP) with reference to proecologic aspects such as using naturally originated photocatalysts, minimalizing volume of the reaction mixture, reactions in aqueous solutions as well as in fruit puree. Taking into consideration a broad range of interests and a number of IPSUM Research Club members, the project consists of numerous syntheses, concentrated on the development of four environmentally friendly synthetic approaches, based on ATRP mechanism. From the application point of view, the result of the project will be the development of innovative, and at the same time inspired by the principles of green chemistry, methods for the synthesis of anionic and cationic polyelectrolytes.

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Project Number: 1/I/2021

Project implemented as part of the “Innovation Incubator 4.0” programme

Title of the project: Synthesis of branched systems with a tannin core for applications as key components of antibacterial and antifouling polymer coatings

Principal Investigator: Prof. Paweł Chmielarz, Eng, PhD, DSc, ProfTit

Project Value: 55 000,00 PLN net

The project is implemented under the program of the Ministry of Science and Education from European funds as part of the non-competition project entitled “Support for the management of scientific research and commercialization of R&D results in research units and enterprises” under the Intelligent Development Operational Program 2014–2020.

Aim of the Project:

The main objective of the project is the synthesis of antifouling and antibacterial polymer materials in the form of star polymers with a tannic acid core using the metal-free ATRP technique in water with a fully biocompatible and economical photoinitiation system - riboflavin (vitamin B2)/ascorbic acid (vitamin C).

The resulting innovative product has potential application as a key component of ecological antifouling and antibacterial paint coatings. An important aspect in the context of paint coatings is also the partial modification of the hydroxyl groups in the structure of tannic acid.

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Project Number: SKN/SP/496557/2021

Project implemented as part of the "Student science clubs create innovation" financed by the Ministry of Science and Education

Title of the project: SI-ATRP in the synthesis of functional polymer brushes grafted from flat surfaces

Principal Investigator: Prof. Paweł Chmielarz, Eng, PhD, DSc, ProfTit

Project Value: 67 135,00 PLN

Financing with resources of Ministry of Science and Education, Poland

Aim of the Project:

The main aim of the project is the synthesis of new, functional polymer materials via surface-initiated radical atomic polymerization (SI-ATRP) methods. The innovative nature of the project assumes the synthesis and characterization of macromolecular compounds and polymer brushes with extensive architecture as well as the optimization of ATRP techniques based on the 12 principles of green chemistry. Due to the wide interest and the number of members of the Student and Doctoral Scientific Society of Chemical and Pharmaceutical Engineering "IPSUM", the project has been divided into 3 parts and includes activities focused on obtaining hybrid materials with potential application in microelectronics (modification of silicon nanoparticles) or implantology (modification of polyetheretherketone) and for biomedical applications, including as carriers of active substances (lignin modification).

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Project Number: UMO-2020/38/E/ST4/00046

Project implemented as part of the SONATA BIS 10 programme

Title of the project: Vitamin B2 as an effective initiator, photoactivator and oxygen scavenger in cost-effective and simplified synthesis of advanced polymer materials by ATRP techniques

Project Promoter: Rzeszow University of Technology, Faculty of Chemistry (Leader), Jagiellonian University, Faculty of Chemistry (Consortium member)

Principal Investigator: Prof. Paweł Chmielarz, Eng, PhD, DSc, ProfTit

Project Value: 1 669 540,00 PLN

Financing with resources of National Science Centre, Poland

Aim of the Project:

In response to “green chemistry” issue a widespread biomolecule – vitamin B2 was selected to serve as a universal and cheap driving force for the synthesis of various polymers by means of variations of ATRP methods. Therefore, the main goal of the project is the investigation of riboflavin (vitamin B2) as a naturally-derived substrate to create a multifunctional molecule playing a few roles simultaneously in the polymerization process, namely as an initiator, photoactivator and oxygen scavenger in the preparation of functional polymer materials with advanced architectures such as polymer brushes, copolymers and polymer stars.

The project is composed of two main concepts. The first one includes an investigation of riboflavin and modified riboflavin as an efficient photoactivator in surface-initiated metal-free atom transfer radical polymerization (rib-SI-metal-free-ATRP). It is expected that the application of “grafting from” methodology will provide an insight into the polymerization mechanism and initiation selectivity. It is planned to design a special reaction setup for rib-SI-metal-free-ATRP in microliter volumes to synthesize advanced polymeric architectures such as homopolymer, copolymer and gradient polymer brushes on flat surfaces. Such miniaturization may help to develop as a cost-effective method for synthesis of functional coatings where only 10-15 μl of polymerization solution will be used to functionalize 1 cm2 of the inorganic surface.

The other concept includes the use of brominated riboflavin as an amphiphilic ATRP initiator and the function of the unmodified isoalloxazine ring of riboflavin molecule in different ways. The main aim is to study the kinetics of various ATRP techniques in terms of a synthesis of the new types of functional brush-like polymers with riboflavin core and poly(meth)acrylates side chains. The initiation functionality of brominated riboflavin will be tested in externally controlled techniques, i.e. simplified electrochemically-mediated ATRP (seATRP) and ultrasound-mediated ATRP (sono-ATRP) with parts per million (ppm) level of catalyst, and photoinduced ATRP with complete elimination of transition metal complex (metal-free ATRP). The main goal of this part is the use of biphasic conditions by using miniemulsion as a reaction medium, polymerizing both hydrophilic and hydrophobic monomer from the amphiphilic initiator, simultaneously, in open-to-air conditions. Moreover, an amphiphilic initiator may allow reduction or complete elimination of additional surfactant in reaction setup. In riboflavin-mediated metal-free-ATRP, the prepared brominated molecule will be examined simultaneously as an amphiphilic initiator and photoactivator, avoiding the use of a transition metal complex.

The project will allow creating the miniemulsion reaction setup with only the riboflavin-based molecule, monomer, and water as a solvent for simultaneous polymerization of two different monomers leading to multicomponent polymers (e.g. zwitterion molecule, pH- and temperature responsiveness in one structure, etc.). The successful project implementation will help to better understand the mechanism of ATRP techniques mediated by riboflavin as a multifunctional molecule for receiving various functional polymeric materials that are in the field of interest of the broad scientific community. It will deliver a facile, selective, oxygen tolerant, and cost-effective method for both modification of various large area surfaces with functional polymers, and preparation polymers with complex architecture.

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pci_logo.pngProject Number: N2_085

Project implemented as part of the PCI grant program entitled "Podkarpackie Innovation Center"

Title of the project: Synthesis of hydrophobic and antibacterial ecological varnish coatings

Principal Investigator: Prof. Paweł Chmielarz, Eng, PhD, DSc, ProfTit

Project Value: 199 883,53 PLN net

Co-financing of the Project from European Regional Development Fund under Priority Axis No. I "Competitive and innovative economy" from the Regional Operational Program of the Podkarpackie Province for 2014-2020

Aim of the Project:
The subject of the project is the synthesis of hydrophobic and antibacterial varnish coatings based on the structure of naturally-derived structures and methacrylic monomers using atom transfer radical polymerization technique with the regeneration of activators by a chemical reducing agent (ARGET ATRP). Another ecological aspect of this project is the reaction medium of conducted syntheses, namely the dispersion system – a miniemulsion, that enables the polymerization of hydrophobic monomers while eliminating the organic solvent from the reaction system.

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Project Number: 2020/37/N/ST4/01991

Project implemented as part of the PRELUDIUM 19 programme

Title of the project: Synthesis of troxerutin-inspired brush-shaped polymers through ATRP methods with diminished catalyst concentration

Principal Investigator: Dr. Izabela Zaborniak, PhD, Eng.

Principal Supervisor: Prof. Paweł Chmielarz, Eng, PhD, DSc, ProfTit

Project Value: 209 999,00 PLN

Financing with resources of National Science Centre, Poland

Aim of the Project:

Atom transfer radical polymerization (ATRP) is a process belonging to the versatile reversibledeactivation radical polymerization (RDRP) procedures. The essence of ATRP is formation of an equilibrium between a low concentration propagating radicals and a larger number of dormant species. Compared to conventional free radical polymerization the step of radical generation is reversible and occurs by a dynamic redox mechanism. Furthermore, polymers and biopolymers prepared by ATRP are characterized by narrow molecular weight distributions (MWDs) and control over molecular weights (MWs). Moreover it allows site incorporation of functionalities and preparation of well-defined hybrid composites. This technique has had a significant impact on the development of various branches in biotechnology, mostly because of its extensive applications in the preparation of biomaterials based on polymers. The use of ATRP makes it possible to control polymer topology and obtain various structures, ranging from linear chains, stars, cycles, combs and brushes, up to regular networks. This technique also allows preparation of polymers with controlled composition such as block, graft, gradient and periodic copolymers. The main disadvantage of the initially developed “normal” ATRP was the use of a relatively high concentration of catalyst, often between 1000-10000 ppm, calculated as the molar ratio of catalyst complex to monomer. Consequently, extensive purification was required, which generates higher process costs for the products. Initially, a high concentration of activator complex was necessary to overcome the increase in concentration of deactivator due to the termination reactions, which led to a slow-down in the rate of the reaction. This problem was resolved by the development of new ATRP methods based on activator regeneration, which allow for significantly diminished concentrations of the catalyst, down to 100 ppm or less. In these methods creation of an additional redox cycle regenerates the activator by reduction of the deactivator. The headline aim of the research project is the optimization of the synthesis of novel naturally-derived stimuli-responsive polymer brushes using low ppm ATRP techniques based on continuous regeneration of catalyst complex, starting from supplemental activation reducing agent (SARA) ATRP utilizing copper as a reducing agent in organic solvent, moving to more environmentally friendly reaction medium – miniemulsion, using activator regeneration by electron transfer (ARGET) ATRP and external stimuli to regenerate catalytic complex, including ultrasonication-induced ATRP (sono-ATRP) in which, under the ultrasonic waves in the aqueous environment, hydroxyl radicals are created constituting the factor leading to the regeneration of Cu (I), without necessity of introducing any additional chemical compound making this technique extremely pure in context to current art of state in low ppm ATRP techniques. The realisation of the project in particular relies on kinetic analysis of the electrochemical catalytic process (EC’) during reduction of the regenerated CuIIBr2/TPMA in the presence of the received ATRP troxerutin-based macroinitiator (Trox-Br10) and subsequently detailed cognition of mechanism and kinetics of polymerization processes with the use of that brominated macromolecule. An another significant aspect of the research is also particular comprehension of the mechanism and kinetics of ATRP syntheses determining the reaction rate constants of particular partial reactions and investigation of chemical structure of the obtained polymer brushes. In connection with the innovation nature of the synthesized biopolymer and also providing novel information related to mechanism and kinetics of conducted reactions, the realisation of the presented project will certainly lead to development of important scientific domain such as Polymer, Biopolymer Chemistry being a part of the domain of scientific research ST - Science and Technology. It is assumed that these troxerutin-based brushes will be ensure flow control of substances in and out in connection to significant pH response due to anionic poly(acrylic acid) (PAA) segments and cationic poly(2-dimethylaminoethyl methacrylate) side chains, additionally the macromolecules are nonimmunogenic, nontoxic and biocompatible, which undoubtedly allow for wide potential application in medicine as stimuli-sensitive drug carriers. Taking into account the fact that troxerutin is used as a vasoprotective, this modified structure can improve its activity or be a carrier for this structure.

 

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Project Number: PPI/PRO/2019/1/00044/U/00001

Project implemented as part of the PROM programme

Title of the project: International scholarship exchange of PhD candidates and academic staff

  1. Synthesis of naturally-derived polymers with different architecture via low ppm atom transfer radical polymerization (ATRP) techniques
  2. Synthesis of poly (tert-butyl acrylate) (PtBA) brushes grafted from the surface of silicon wafers using the sono-ATRP technique in miniemulsion

Principal Investigator: Prof. Paweł Chmielarz, Eng, PhD, DSc, ProfTit

Project Value: 44 400,00 PLN

Co-financing of the Project from European Regional Social Fund and Polish National Agency for Academic Exchange

Aim of the Project:

The aim of the project is to create a mechanism of financial support for scholarship exchange of PhD candidates and academic staff programmes.  These programmes will enable participation in short forms of education (lasting from 5 to 30 days) which are aimed at increasing competences and qualifications. The project will contribute to the improvement of accessibility of international education programmes and will increase the mobility of the personnel both in the field of visits of representatives of Polish universities and scientific institutions abroad as well as arrivals of scholarship holders to Poland, including people from outside the EU.

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Project Number: POIR.04.01.01-00-0002/16-00

Project Promoter: Warsaw University of Technology, Faculty of Chemistry (Leader), Rzeszów University of Technology, Faculty of Chemistry (Consortium member)

Principal Investigator: prof. dr hab. inż. Zbigniew Florjańczyk

Project Value: 3 677 784,00 PLN

Co-financing of the Project from European Regional Development Fund under the Smart Growth Operational Programme: 1 838 892,00 PLN

Aim of the Project:
The project will result in the elaboration of a method of manufacturing of four types of products enabling gluing various types of materials (metals, glass, some types of plastics). The basic components of these systems will be polyurethane glues and sealants cured with moisture from the air. In order to achieve joints of good mechanical properties and high resistance to atmospheric factors, a new type of oligomerols containing in their structure carbonate groups and aliphatic?aromatic ester groups derived from waste poly(ethylene therephthalate) will be utilized for the preparation of urethane prepolymers. The aim of further studies will be to change the curing mechanism of prepolymers to eliminate the hydrolysis of isocyanate groups resulting in carbon dioxide evolution causing foaming of joints. One possible solution to this problem is the introduction of silanol groups to the prepolymer structure; in presence of moisture these groups undergo hydrolysis and condensation forming polymer networks. Such type of materials will be also applied as prime coatings capable of chemical bonding with some glued materials. The second solution needed mainly for the preparation of sealants involves the use of reactive solvents, which in reaction with moisture will generate functional groups reacting with isocyanate groups of prepolymers without CO2 evolution. To assure the appropriate rheological conditions and improved chemical resistance and other functional parameters, the urethane prepolymers will be additionally modified with fillers, pigments, surfactants and UV stabilizers.