The increase in conductivity with temperature in 1H-pyrazol-2-ium 2,6-dicarboxybenzoate monohydra... more The increase in conductivity with temperature in 1H-pyrazol-2-ium 2,6-dicarboxybenzoate monohydrate was analyzed, and the influence of the mobility of the water was discussed in this study. The electric properties of the salt were studied using the impedance spectroscopy method. WB97XD/6-311++G(d,p) calculations were performed, and the quantum theory of atoms in molecules (QTAiM) approach and the Hirshfeld surface method were applied to analyze the hydrogen bond interaction. It was found that temperature influences the spectroscopic properties of pyrazolium salt, particularly the carbonyl and hydroxyl frequencies. The influence of water molecules, connected by three-center hydrogen bonds with co-planar tetrameters, on the formation of structural defects is also discussed in this report.
Proceedings of the 5th World Congress on New Technologies, 2019
Environment contamination by heavy metals cause serious health and ecological problems in many pa... more Environment contamination by heavy metals cause serious health and ecological problems in many parts of the world [1]. Therefore, their accurate analytical determination is of great importance. Chemical modification of electrodes is an effective way to improve sensitivity and selectivity of electrochemical sensors used for metal ions determination. Carbon nanotubes (CNTs) due to their high electrical conductivity can introduce strong electrocatalytic activity to electrochemical devices, and thus, have been successfully applied in the fabrication of electrochemical sensors for various applications [2]. Ion-imprinted polymers (IIPs) are macromolecules showing high selectivity toward target ion related to a memory effect resulting from the process of their preparation. Their other advantages are chemical stability, low cost, and easiness of preparation [3]. Carbon nanotubes functionalized with ion-imprinted polymers are promising materials for electrodes modification. The aim of the study is formation of new selective materials based on carbon nanotubes and ion-imprinted polymers for modification of electrodes. The first stage of the project involved covalent functionalization of carbon nanotubes with dithiocarbonates, which are chain transfer agents in RAFT (reversible addition-fragmentation chain transfer) polymerization. Functionalization of CNTs with dithiocarbonates enables polymerization conducted directly from nanotube's surface. CNT-IIP hybrids were synthesized by polymerizing a mixture of dithiocarbonate-modified CNTs, template ions (Pd 2+), functional monomers and a crosslinker. Polymerizations were performed using commercially available monomers (e.g. acrylonitrile, acrylic acid) as well as synthesized ones i.e. carbamohydrazonothioate or thiourea-based molecules having high affinity to metal ions. In this way several CNT-IIP nanohybrids were obtained. The specific cavities complementary to the size and shape of the template ions were formed after their removal from the polymer network. The obtained materials were deposited on gold electrodes by solvent evaporation. Raman spectroscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, and scanning and transmission electron microscopy were employed to confirm modifications and study chemical composition of the obtained materials. Electrochemical properties were analysed by cyclic voltammetry and electrochemical impedance spectroscopy.
The structural studies of carbamohydrazonothioate derivative and its hydrochloride solvate are th... more The structural studies of carbamohydrazonothioate derivative and its hydrochloride solvate are the aim of hereunder presented research. The combination of the crystallographic technics and the Hirshfeld surface analysis allows to describe the net of the hydrogen bonds as well as other non-covalent interactions within the crystal structures. The crystal structures of 4-ethenylbenzyl N ′-[(E)-phenylmethylidene] carbamohydrazonothioate (CHT) and CHT hydrochloride solvate are built of bent and linear conformers of the carbamohydrazonothioate derivative, respectively. The theoretical calculations indicate that the alteration of the conformation is possible. While the geometry of the bent conformers allows the crystal structure to propagate, the linear conformation does not encourage formation of the intermolecular interactions between CHT molecules. Therefore, in the latter case, the chloride ions and methanol play the role of the molecular glue. In both crystal structures, the dominant is H•••H interaction; thus, the dispersion energy is an important factor in intermolecular interactions. The theoretical calculations for single molecules and dimers of CHT show the negligible influence of the crystal packing on molecular conformation and dimer formation, when the dispersion energy correction is applied.
Complexing and easily separable polymer–magnetic nanohybrids based on iron oxide nanoparticles an... more Complexing and easily separable polymer–magnetic nanohybrids based on iron oxide nanoparticles and original carbamohydrazonothioate derivatives.
Thorough understanding of magnetic nanoparticle (MNP) properties is essential for developing new ... more Thorough understanding of magnetic nanoparticle (MNP) properties is essential for developing new theranostics. In this study we provide evidence that non-modified magnetic iron oxide nanoparticles and their functionalized derivatives may be used to restrict growth and capture different pathogens. Coprecipitation of Fe 2+ and Fe 3+ ions in an alkaline solution was used to synthesize MNPs that subsequently were functionalized by gold and aminosilane coating. Transmission electron microscopy (TEM), differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FT-IR) were used to assess their physicochemical properties. A significant decrease of Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa and Candida albicans outgrown from medium after addition of MNPs or their derivatives was observed during 24h culture. Measurement of optical density revealed that using MNPs, these pathogens can be quickly captured and removed (with efficiency reaching almost 100%) from purposely infected saline buffer and body fluids such as human blood plasma, serum, abdominal fluids and cerebrospinal fluids. These effects depend on nanoparticle concentration, surface chemistry, the type of pathogen, as well as the surrounding environment.
This study shows that covalently immobilizing triazine-based structures on spherical carbon nanos... more This study shows that covalently immobilizing triazine-based structures on spherical carbon nanostructures results in the organization of micro- and mesopores in a three-dimensional manner. We selected the nitrile-functionalized pyrrolo[3,2-b]pyrrole unit to form triazine rings to construct a covalent organic framework. Combining spherical carbon nanostructures with the triazine framework produced a material with unique physicochemical properties, exhibiting the highest specific capacitance value of 638 F g-1 in aqueous acidic solutions. This phenomenon is attributed to many factors. The material exhibits a large surface area, a high content of micropores, a high content of graphitic N, and N-sites with basicity and semi-crystalline character. The hybrid systems containing triazines and carbon nano-onions were, for the first time, used as electrodes for supercapacitors. Thanks to the high structural organization and reproducibility, and remarkably high specific capacitance, these sy...
The organization of specific pores in carbonaceous three-dimensional networks is crucial for effi... more The organization of specific pores in carbonaceous three-dimensional networks is crucial for efficient electrocatalytic processes and electrochemical performance. Therefore, the synthesis of porous materials with ordered and well-defined pores is required in this field. The incorporation of carbon nanostructures into polymers can create material structures that are more ordered in comparison to those of the pristine polymers. In this study we applied polymer-templated methods of carbon material preparation, in which outer blocks of the star copolymers form the carbon skeleton, while the core part is pore-forming. Well-defined 6-star-(poly(methyl acrylate)-b-poly(4-acetoxystyrene)) dendrimers were synthesized by reversible addition−fragmentation chain-transfer polymerization. They were then transformed into poly(4-vinylphenol) derivatives (namely 6-star-(poly(methyl acrylate)-b-poly(4vinylphenol)), subjected to polycondensation with formaldehyde, and pyrolyzed at 800°C. Cross-linking of phenolic groups provides a polymer network that does not depolymerize by pyrolysis, unlike poly(methyl acrylate) chains. The selected star polymers were attached to carbon nano-onions (CNOs) to improve the organization of the polymer chains. Herein, the physicochemical properties of CNO-polymer hybrids, including the textural and the electrochemical properties, were compared with those of the pristine pyrolyzed polymers obtained under analogous experimental conditions. For these purposes, we used several experimental and theoretical methods, such as infrared, Raman, and X-ray photoelectron spectroscopy, nitrogen adsorption/desorption measurements, scanning and transmission electron microscopy, and electrochemical studies, including cyclic voltammetry. All of the porous materials were evaluated for use as supercapacitors.
As one of the main consumables of interior decoration and furniture, decorative paper can be seen... more As one of the main consumables of interior decoration and furniture, decorative paper can be seen everywhere in the indoor space. However, because of its high content of formaldehyde, it has a certain threat to people’s health. Therefore, it is necessary to develop and study new formaldehyde-free decorative paper to meet the market demand. In this work, we have obtained formaldehyde-free decorative paper with high CO2 adsorption capacity. Here, cellulose nanocrystals (CNC) were prepared by hydrolyzing microcrystalline cellulose with sulfuric acid. The N-(2-aminoethyl) (3-amino-propyl) methyldimethoxysilane (AEAPMDS) was grafted onto the CNCs by liquid phase hydrothermal treatment, and the aqueous solution was substituted by tert-butanol to obtain aminated CNCs (AEAPMDS-CNCs). The as-prepared AEAPMDS-CNCs were applied to formaldehyde-free decorative paper by the spin-coating method. The effects of various parameters on the properties of synthetic materials were systematically studied...
This review aims to provide an overview of polymers comprising cholesterol moiety/ies designed to... more This review aims to provide an overview of polymers comprising cholesterol moiety/ies designed to be used in drug delivery. Over the last two decades, there have been many papers published in this field, which are summarized in this review. The primary focus of this article is on the methods of synthesis of polymers bearing cholesterol in the main chain or as side chains. The data related to the composition, molecular weight, and molecular weight distribution of polymers are presented. Moreover, other aspects, such as forms of carriers, types of encapsulated drugs, encapsulation efficiency and capacity, are also included.
The aim of this study was to get an overview of current theory and practice in early assessments ... more The aim of this study was to get an overview of current theory and practice in early assessments of medical devices, and to identify aims and uses of early assessment methods used in practice. Methods: A systematic literature review was conducted in September 2013, using computerized databases (PubMed, Science Direct, and Scopus), and references list search. Selected articles were categorized based on their type, objective, and main target audience. The methods used in the application studies were extracted and mapped throughout the early stages of development and for their particular aims. Results: Of 1,961 articles identified, eighty-three studies passed the inclusion criteria, and thirty were included by searching reference lists. There were thirty-one theoretical papers, and eighty-two application papers included. Most studies investigated potential applications/possible improvement of medical devices, developed early assessment framework or included stakeholder perspective in early development stages. Among multiple qualitative and quantitative methods identified, only few were used more than once. The methods aim to inform strategic considerations (e.g., literature review), economic evaluation (e.g., cost-effectiveness analysis), and clinical effectiveness (e.g., clinical trials). Medical devices were often in the prototype product development stage, and the results were usually aimed at informing manufacturers. Conclusions: This study showed converging aims yet widely diverging methods for early assessment during medical device development. For early assessment to become an integral part of activities in the development of medical devices, methods need to be clarified and standardized, and the aims and value of assessment itself must be demonstrated to the main stakeholders for assuring effective and efficient medical device development.
The increase in conductivity with temperature in 1H-pyrazol-2-ium 2,6-dicarboxybenzoate monohydra... more The increase in conductivity with temperature in 1H-pyrazol-2-ium 2,6-dicarboxybenzoate monohydrate was analyzed, and the influence of the mobility of the water was discussed in this study. The electric properties of the salt were studied using the impedance spectroscopy method. WB97XD/6-311++G(d,p) calculations were performed, and the quantum theory of atoms in molecules (QTAiM) approach and the Hirshfeld surface method were applied to analyze the hydrogen bond interaction. It was found that temperature influences the spectroscopic properties of pyrazolium salt, particularly the carbonyl and hydroxyl frequencies. The influence of water molecules, connected by three-center hydrogen bonds with co-planar tetrameters, on the formation of structural defects is also discussed in this report.
Proceedings of the 5th World Congress on New Technologies, 2019
Environment contamination by heavy metals cause serious health and ecological problems in many pa... more Environment contamination by heavy metals cause serious health and ecological problems in many parts of the world [1]. Therefore, their accurate analytical determination is of great importance. Chemical modification of electrodes is an effective way to improve sensitivity and selectivity of electrochemical sensors used for metal ions determination. Carbon nanotubes (CNTs) due to their high electrical conductivity can introduce strong electrocatalytic activity to electrochemical devices, and thus, have been successfully applied in the fabrication of electrochemical sensors for various applications [2]. Ion-imprinted polymers (IIPs) are macromolecules showing high selectivity toward target ion related to a memory effect resulting from the process of their preparation. Their other advantages are chemical stability, low cost, and easiness of preparation [3]. Carbon nanotubes functionalized with ion-imprinted polymers are promising materials for electrodes modification. The aim of the study is formation of new selective materials based on carbon nanotubes and ion-imprinted polymers for modification of electrodes. The first stage of the project involved covalent functionalization of carbon nanotubes with dithiocarbonates, which are chain transfer agents in RAFT (reversible addition-fragmentation chain transfer) polymerization. Functionalization of CNTs with dithiocarbonates enables polymerization conducted directly from nanotube's surface. CNT-IIP hybrids were synthesized by polymerizing a mixture of dithiocarbonate-modified CNTs, template ions (Pd 2+), functional monomers and a crosslinker. Polymerizations were performed using commercially available monomers (e.g. acrylonitrile, acrylic acid) as well as synthesized ones i.e. carbamohydrazonothioate or thiourea-based molecules having high affinity to metal ions. In this way several CNT-IIP nanohybrids were obtained. The specific cavities complementary to the size and shape of the template ions were formed after their removal from the polymer network. The obtained materials were deposited on gold electrodes by solvent evaporation. Raman spectroscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, and scanning and transmission electron microscopy were employed to confirm modifications and study chemical composition of the obtained materials. Electrochemical properties were analysed by cyclic voltammetry and electrochemical impedance spectroscopy.
The structural studies of carbamohydrazonothioate derivative and its hydrochloride solvate are th... more The structural studies of carbamohydrazonothioate derivative and its hydrochloride solvate are the aim of hereunder presented research. The combination of the crystallographic technics and the Hirshfeld surface analysis allows to describe the net of the hydrogen bonds as well as other non-covalent interactions within the crystal structures. The crystal structures of 4-ethenylbenzyl N ′-[(E)-phenylmethylidene] carbamohydrazonothioate (CHT) and CHT hydrochloride solvate are built of bent and linear conformers of the carbamohydrazonothioate derivative, respectively. The theoretical calculations indicate that the alteration of the conformation is possible. While the geometry of the bent conformers allows the crystal structure to propagate, the linear conformation does not encourage formation of the intermolecular interactions between CHT molecules. Therefore, in the latter case, the chloride ions and methanol play the role of the molecular glue. In both crystal structures, the dominant is H•••H interaction; thus, the dispersion energy is an important factor in intermolecular interactions. The theoretical calculations for single molecules and dimers of CHT show the negligible influence of the crystal packing on molecular conformation and dimer formation, when the dispersion energy correction is applied.
Complexing and easily separable polymer–magnetic nanohybrids based on iron oxide nanoparticles an... more Complexing and easily separable polymer–magnetic nanohybrids based on iron oxide nanoparticles and original carbamohydrazonothioate derivatives.
Thorough understanding of magnetic nanoparticle (MNP) properties is essential for developing new ... more Thorough understanding of magnetic nanoparticle (MNP) properties is essential for developing new theranostics. In this study we provide evidence that non-modified magnetic iron oxide nanoparticles and their functionalized derivatives may be used to restrict growth and capture different pathogens. Coprecipitation of Fe 2+ and Fe 3+ ions in an alkaline solution was used to synthesize MNPs that subsequently were functionalized by gold and aminosilane coating. Transmission electron microscopy (TEM), differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FT-IR) were used to assess their physicochemical properties. A significant decrease of Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa and Candida albicans outgrown from medium after addition of MNPs or their derivatives was observed during 24h culture. Measurement of optical density revealed that using MNPs, these pathogens can be quickly captured and removed (with efficiency reaching almost 100%) from purposely infected saline buffer and body fluids such as human blood plasma, serum, abdominal fluids and cerebrospinal fluids. These effects depend on nanoparticle concentration, surface chemistry, the type of pathogen, as well as the surrounding environment.
This study shows that covalently immobilizing triazine-based structures on spherical carbon nanos... more This study shows that covalently immobilizing triazine-based structures on spherical carbon nanostructures results in the organization of micro- and mesopores in a three-dimensional manner. We selected the nitrile-functionalized pyrrolo[3,2-b]pyrrole unit to form triazine rings to construct a covalent organic framework. Combining spherical carbon nanostructures with the triazine framework produced a material with unique physicochemical properties, exhibiting the highest specific capacitance value of 638 F g-1 in aqueous acidic solutions. This phenomenon is attributed to many factors. The material exhibits a large surface area, a high content of micropores, a high content of graphitic N, and N-sites with basicity and semi-crystalline character. The hybrid systems containing triazines and carbon nano-onions were, for the first time, used as electrodes for supercapacitors. Thanks to the high structural organization and reproducibility, and remarkably high specific capacitance, these sy...
The organization of specific pores in carbonaceous three-dimensional networks is crucial for effi... more The organization of specific pores in carbonaceous three-dimensional networks is crucial for efficient electrocatalytic processes and electrochemical performance. Therefore, the synthesis of porous materials with ordered and well-defined pores is required in this field. The incorporation of carbon nanostructures into polymers can create material structures that are more ordered in comparison to those of the pristine polymers. In this study we applied polymer-templated methods of carbon material preparation, in which outer blocks of the star copolymers form the carbon skeleton, while the core part is pore-forming. Well-defined 6-star-(poly(methyl acrylate)-b-poly(4-acetoxystyrene)) dendrimers were synthesized by reversible addition−fragmentation chain-transfer polymerization. They were then transformed into poly(4-vinylphenol) derivatives (namely 6-star-(poly(methyl acrylate)-b-poly(4vinylphenol)), subjected to polycondensation with formaldehyde, and pyrolyzed at 800°C. Cross-linking of phenolic groups provides a polymer network that does not depolymerize by pyrolysis, unlike poly(methyl acrylate) chains. The selected star polymers were attached to carbon nano-onions (CNOs) to improve the organization of the polymer chains. Herein, the physicochemical properties of CNO-polymer hybrids, including the textural and the electrochemical properties, were compared with those of the pristine pyrolyzed polymers obtained under analogous experimental conditions. For these purposes, we used several experimental and theoretical methods, such as infrared, Raman, and X-ray photoelectron spectroscopy, nitrogen adsorption/desorption measurements, scanning and transmission electron microscopy, and electrochemical studies, including cyclic voltammetry. All of the porous materials were evaluated for use as supercapacitors.
As one of the main consumables of interior decoration and furniture, decorative paper can be seen... more As one of the main consumables of interior decoration and furniture, decorative paper can be seen everywhere in the indoor space. However, because of its high content of formaldehyde, it has a certain threat to people’s health. Therefore, it is necessary to develop and study new formaldehyde-free decorative paper to meet the market demand. In this work, we have obtained formaldehyde-free decorative paper with high CO2 adsorption capacity. Here, cellulose nanocrystals (CNC) were prepared by hydrolyzing microcrystalline cellulose with sulfuric acid. The N-(2-aminoethyl) (3-amino-propyl) methyldimethoxysilane (AEAPMDS) was grafted onto the CNCs by liquid phase hydrothermal treatment, and the aqueous solution was substituted by tert-butanol to obtain aminated CNCs (AEAPMDS-CNCs). The as-prepared AEAPMDS-CNCs were applied to formaldehyde-free decorative paper by the spin-coating method. The effects of various parameters on the properties of synthetic materials were systematically studied...
This review aims to provide an overview of polymers comprising cholesterol moiety/ies designed to... more This review aims to provide an overview of polymers comprising cholesterol moiety/ies designed to be used in drug delivery. Over the last two decades, there have been many papers published in this field, which are summarized in this review. The primary focus of this article is on the methods of synthesis of polymers bearing cholesterol in the main chain or as side chains. The data related to the composition, molecular weight, and molecular weight distribution of polymers are presented. Moreover, other aspects, such as forms of carriers, types of encapsulated drugs, encapsulation efficiency and capacity, are also included.
The aim of this study was to get an overview of current theory and practice in early assessments ... more The aim of this study was to get an overview of current theory and practice in early assessments of medical devices, and to identify aims and uses of early assessment methods used in practice. Methods: A systematic literature review was conducted in September 2013, using computerized databases (PubMed, Science Direct, and Scopus), and references list search. Selected articles were categorized based on their type, objective, and main target audience. The methods used in the application studies were extracted and mapped throughout the early stages of development and for their particular aims. Results: Of 1,961 articles identified, eighty-three studies passed the inclusion criteria, and thirty were included by searching reference lists. There were thirty-one theoretical papers, and eighty-two application papers included. Most studies investigated potential applications/possible improvement of medical devices, developed early assessment framework or included stakeholder perspective in early development stages. Among multiple qualitative and quantitative methods identified, only few were used more than once. The methods aim to inform strategic considerations (e.g., literature review), economic evaluation (e.g., cost-effectiveness analysis), and clinical effectiveness (e.g., clinical trials). Medical devices were often in the prototype product development stage, and the results were usually aimed at informing manufacturers. Conclusions: This study showed converging aims yet widely diverging methods for early assessment during medical device development. For early assessment to become an integral part of activities in the development of medical devices, methods need to be clarified and standardized, and the aims and value of assessment itself must be demonstrated to the main stakeholders for assuring effective and efficient medical device development.
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Papers by Karolina Markiewicz